Ultraviolet-curable composition and recorded matter

ABSTRACT

An ultraviolet-curable composition is discharged with an ink jet method and includes a polymerizable compound; a metal powder; and a thixotropy suppressing agent, in which a relationship of η2−η1≤3 is satisfied between a viscosity η1 [mPa·s] at a shearing speed of 1000 sec−1 and a viscosity η2 [mPa·s] which is determined by measuring in a state where the shearing speed is 10 sec−1 after continuing to add shearing stress for 10 minutes at the shearing speed of 1000 sec−1.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.15/342,452, filed on Nov. 3, 2016, which claims priority to JapanesePatent Application No. 2015-224702, filed on Nov. 17, 2015. The entiredisclosures of both of the above applications are hereby expresslyincorporated by reference herein.

BACKGROUND 1. Technical Field

The present invention relates to an ultraviolet-curable composition andrecorded matter.

2. Related Art

In the background art, as methods for manufacturing ornaments which haveglossiness, metal plating, stamping printing using a metal foil, thermaltransfer using a metal foil, and the like are used.

However, there is a problem with these methods in that fine patternformation and application to curved portions are difficult.

On the other hand, a recording method in which a composition including apigment or dye is applied to a recording medium with an ink jet methodcan be used. This method is excellent in the points that fine patternformation is possible and that suitable application for recording oncurved portions is also possible. In addition, in recent years,compositions which are cured when irradiated with ultraviolet rays(ultraviolet-curable compositions) have been used (for example, refer toJP-A-2009-57548) in order to obtain particularly excellent abrasionresistance, water resistance, solvent resistance, and the like.

However, in a case of simply applying a metal powder instead of apigment or dye, there is a problem in that the liquid droplet dischargestability is poor with an ink jet method, discharge failures are easilygenerated, and it is not possible to sufficiently exhibitcharacteristics such as the natural glossiness of the metal.

SUMMARY

An advantage of some aspects of the invention is to provide anultraviolet-curable composition which is excellent in dischargestability with an ink jet method and which is able to stably form apattern (a printed portion) with excellent glossiness, and also toprovide recorded matter which has a pattern (a printed portion) withexcellent glossiness.

The invention has adopted the following.

According to an aspect of the invention, an ultraviolet-curablecomposition discharged by an ink jet method includes a polymerizablecompound, a metal powder, and a thixotropy suppressing agent, in which arelationship of η2−η1≤3 is satisfied between a viscosity η1 [mPa·s] at ashearing speed of 1000 sec⁻¹ and a viscosity η2 [mPa·s] obtained bymeasuring in a state where the shearing speed is set as 10 sec⁻¹ aftercontinuously adding shearing stress for 10 minutes at the shearing speedof 1000 sec⁻¹.

Due to this, it is possible to provide an ultraviolet-curablecomposition which is excellent in discharge stability with an ink jetmethod and which is able to stably form a pattern (a printed portion)with excellent glossiness.

In the ultraviolet-curable composition according to the aspect of theinvention, one type or two or more types selected from a group formed ofa phosphoric acid-based dispersing agent, an alkyl amine-baseddispersing agent, and fluorine-containing powder are preferably includedas the thixotropy suppressing agent.

Due to this, it is possible to make the discharge stability of theultraviolet-curable composition with an ink jet method particularlyexcellent. In addition, it is possible to make the glossiness, theabrasion resistance, and the like of the recorded matter particularlyexcellent while making the productivity of the recorded matter and thereliability of the recorded matter excellent.

In the ultraviolet-curable composition according to the aspect of theinvention, the content ratio of the thixotropy suppressing agent in theultraviolet-curable composition is preferably 0.2 mass % to 2.0 mass %.

Due to this, it is possible to make the discharge stability of theultraviolet-curable composition with an ink jet method particularlyexcellent and make the productivity of the recorded matter and thereliability of the recorded matter particularly excellent, and it isalso possible to make the glossiness, the abrasion resistance, and thelike of the recorded matter particularly excellent.

In the ultraviolet-curable composition according to the aspect of theinvention, the metal powder is preferably subjected to a surfacetreatment.

Due to this, it is possible to increase the dispersion stability of themetal powder (particles) in the ultraviolet-curable composition and itis possible to make the storage stability and the like of theultraviolet-curable composition particularly excellent. In addition, aproblem in that discharge failures with an ink jet method are easilygenerated occurs more remarkably in a case where the constituentparticles of the metal powder are subjected to a surface treatment by asurface treatment agent; however, in the invention, it is possible tostably discharge the ultraviolet-curable composition with an ink jetmethod over a long period even in a case where the constituent particlesof the metal powder are subjected to a surface treatment by a surfacetreatment agent. That is, the effects according to the aspect of theinvention are more remarkably exhibited in a case where the constituentparticles of the metal powder are subjected to a surface treatment by asurface treatment agent.

In the ultraviolet-curable composition according to the aspect of theinvention, the surface treatment is preferably performed using afluorine-based surface treatment agent.

Due to this, it is possible to make the storage stability of theultraviolet-curable composition particularly excellent. In addition, inthe recorded matter produced using the ultraviolet-curable composition,it is possible to more effectively exhibit characteristics such as thenatural glossiness of the metal material which forms the metal powder.In addition, it is possible to make the abrasion resistance of a printedportion of the recorded matter particularly excellent and to moreeffectively prevent changes in appearance due to friction (for example,a decrease in the glossiness, a decrease in aesthetics (aestheticappearance), and the like).

In the ultraviolet-curable composition according to the aspect of theinvention, the fluorine-based surface treatment agent is preferably onetype or two or more types selected from a group formed of afluorine-based silane compound, a fluorine-based phosphate compound, afluorine-substituted fatty acid, and a fluorine-based isocyanatecompound.

Due to this, it is possible to make the discharge stability of theultraviolet-curable composition with an ink jet method particularlyexcellent and to make the productivity of the recorded matter and thereliability of the recorded matter particularly excellent. In addition,it is possible to make the glossiness, the abrasion resistance, and thelike of the recorded matter particularly excellent.

In the ultraviolet-curable composition according to the aspect of theinvention, the average particle diameter of the metal powder ispreferably 200 nm to 3.0 μm.

Due to this, it is possible to make the glossiness and sense of luxuryof the recorded matter produced using the ultraviolet-curablecomposition particularly excellent. In addition, it is possible to makethe storage stability and discharge stability of the ultraviolet-curablecomposition superior.

In the ultraviolet-curable composition according to the aspect of theinvention, the metal powder preferably includes constituent particleswhere at least a surface is mainly formed of Al.

Due to this, it is possible to make the storage stability of theultraviolet-curable composition particularly excellent. In addition, itis possible to make the glossiness and sense of luxury of the recordedmatter particularly excellent while suppressing increases in theproduction cost of the recorded matter. In addition, Al naturally hasparticularly excellent glossiness among various types of metalmaterials; however, the present inventors discovered that the problem ofdecreases in the discharge stability with an ink jet method or the likeoccurs particularly easily in a case of trying to apply particles whichare formed of Al to the ultraviolet-curable composition. In contrast, inthe invention, it is possible to reliably prevent the occurrence of theproblem described above even in a case of using particles which areformed of Al. That is, the effects according to the aspect of theinvention are more remarkably exhibited in a case where the metalmaterial which forms the metal powder is mainly formed of Al.

In the ultraviolet-curable composition according to the aspect of theinvention, the constituent particles of the metal powder are preferablyflaky.

Due to this, it is possible to effectively exhibit the naturalglossiness or the like of the metal material which forms the metalpowder even in the obtained recorded matter, and it is possible to makethe glossiness and sense of luxury of a formed pattern (a printedportion) particularly excellent. In addition, the problem in thebackground art that the discharge stability with an ink jet methoddecreases occurs particularly remarkably in a case of using a metalpowder which includes flaky particles; however, in the invention, it ispossible to effectively prevent the occurrence of the problem describedabove even when the particles which form the metal powder are flaky.That is, the effects according to the aspect of the invention are moreremarkably exhibited in a case where the particles which form the metalpowder are flaky.

In the ultraviolet-curable composition according to the aspect of theinvention, the average thickness of the constituent particles of themetal powder is preferably 10 nm to 80 nm.

Due to this, it is possible to make the glossiness and sense of luxuryof the formed pattern (the printed portion) superior.

In The ultraviolet-curable composition according to the aspect of theinvention, a monomer which has an alicyclic structure is preferablyincluded as the polymerizable compound.

Due to this, it is possible to make the storage stability and dischargestability of the ultraviolet-curable composition particularly excellent,and it is also possible to make the glossiness and abrasion resistanceof the printed portion of the recorded matter produced using theultraviolet-curable composition particularly excellent.

In the ultraviolet-curable composition according to the aspect of theinvention, the monomer having an alicyclic structure preferably includesone or more types selected from a group formed oftris(2-acryloyloxyethyl) isocyanurate, dicyclopentenyloxyethyl acrylate,adamantyl acrylate, γ-butyrolactone acrylate, N-vinylcaprolactam,N-vinylpyrrolidone, pentamethylpiperidyl acrylate, tetramethylpiperidylacrylate, 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl acrylate,mevalonic lactone acrylate, dimethylol tricyclodecane diacrylate,dimethylol dicyclopentane diacrylate, dicyclopentenyl acrylate, dicyclopentanyl acrylate, isobornyl acrylate, cyclohexyl acrylate,acryloylmorpholine, tetrahydrofurfuryl acrylate, cyclohexanespiro-2-(1,3-dioxolan-4-yl) methyl acrylate, and(2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate.

Due to this, it is possible to make the glossiness and sense of luxuryof the recorded matter produced using the ultraviolet-curablecomposition superior. In addition, it is possible to make the storagestability and discharge stability of the ultraviolet-curable compositionsuperior.

In the ultraviolet-curable composition according to the aspect of theinvention, one type or two or more types selected from a group formed ofphenoxyethyl acrylate, benzyl acrylate, 2-(2-vinyloxy ethoxy) ethylacrylate, dipropylene glycol diacrylate, tripropylene glycol diacrylate,2-hydroxy 3-phenoxypropyl acrylate, and 4-hydroxybutyl acrylate arepreferably included as the polymerizable compound other than the monomerhaving an alicyclic structure.

Due to this, it is possible to make the reactivity of theultraviolet-curable composition after discharge with the ink jet methodparticularly excellent while making the storage stability and dischargestability of the ultraviolet-curable composition particularly excellent,to make the productivity of the recorded matter particularly excellent,and to make the abrasion resistance and the like of the formed patternsparticularly excellent.

The recorded matter according to another aspect of the invention isprovided with a cured product of the ultraviolet-curable compositionaccording to the aspect of the invention described above, and arecording medium.

Due to this, it is possible to provide recorded matter with excellentglossiness and which has a pattern (printed portion) where thegeneration of defects is prevented.

DESCRIPTION OF EXEMPLARY EMBODIMENTS

Detailed description will be given below of favorable embodiments of theinvention.

Ultraviolet-Curable Composition

First, description will be given of the ultraviolet-curable compositionaccording to an aspect of the invention.

The ultraviolet-curable composition of the invention includes apolymerizable compound which is polymerized by being irradiated withultraviolet rays, and a metal powder.

Here, in the background art, metal plating, stamping printing using ametal foil, thermal transfer using a metal foil, and the like are usedas methods for manufacturing ornaments which have glossiness.

However, there is a problem with these methods in that fine patternformation and application to curved portions is difficult.

On the other hand, a recording method in which a composition including apigment or dye is applied to a recording medium with an ink jet methodcan be used. This method is excellent in the points of fine patternformation and that suitable application to curved portions is alsopossible. In addition, in recent years, compositions which are curedwhen irradiated with ultraviolet rays (ultraviolet-curable compositions)have been used in order to obtain particularly excellent abrasionresistance, water resistance, solvent resistance, and the like.

However, in a case of simply applying a metal powder instead of apigment or dye, there is a problem in that the liquid droplet dischargestability is poor with an ink jet method, discharge failures are easilygenerated, and it is not possible to sufficiently exhibitcharacteristics such as the natural glossiness of the metal.

Thus, the present inventors completed the invention as a result ofintensive research focusing particularly on the state of theultraviolet-curable composition in an ink jet head for the purpose ofsolving the problem described above. That is, the ultraviolet-curablecomposition (an ultraviolet-curable ink jet composition) of theinvention includes a polymerizable compound, metal powder, and athixotropy suppressing agent, and satisfies a relationship of η2−η1≤3between a viscosity η1 [mPa·s] at a shearing speed of 1000 sec⁻¹ and aviscosity η2 [mPa·s] obtained by measuring in a state where the shearingspeed is set as 10 sec⁻¹ after continuously adding shearing stress for10 minutes at a shearing speed of 1000 sec⁻¹.

It may be considered that these excellent effects can be obtained forthe reasons below. That is, although a large amount of stress (shearingstress) is added to the ultraviolet-curable composition in an ink jethead in an extremely short period, the amount of the liquid dropletswhich are discharged from nozzles of the ink jet head is extremelysmall. Accordingly, the ultraviolet-curable composition which issupplied in the ink jet head repeatedly and discontinuously receives alarge amount stress (shearing stress) a plurality of times insynchronization with changes in the ink usage amount up to the dischargefrom the nozzles. Under these circumstances, particles of the metalpowder which is included in the ultraviolet-curable composition are in astate of being rubbed together in the flow which is generated accordingto a flow path shape inside the ink jet head and the distance betweenthe particles is often momentarily extremely close at places where theflow is fast and the shearing stress is large, such as inside the inkjet head. As a result, since a pigment subjected to a fluorine-basedsurface treatment has a property of tending to be stable in a statewhere the particles are aggregated and coarsened, the viscosity of theultraviolet-curable composition easily increases inside the ink jet headdue to the structural viscosity. As the result, in theultraviolet-curable composition to which a metal powder is simplyapplied instead of a pigment or dye, discharge failures are easilygenerated since the originally exhibited ink viscosity greatly changesbeyond the allowable range inside the ink jet head. Accordingly, aproblem occurs in that it is not possible to sufficiently exhibitcharacteristics such as the natural glossiness of the metal due to itnot being possible to uniformly form a coated film. In the invention,since including a thixotropy suppressing agent makes it possible for thepigment subjected to fluorine-based surface treatment to quicklydissolve and aggregate due to the effect of the thixotropy suppressingagent even after a large amount of shearing stress is added over a longperiod, it is possible to effectively prevent aggregation of the metalpowder and increase the viscosity of the ultraviolet-curablecomposition, to maintain the discharge stability of the liquid dropletswith the ink jet method over a long period, and to sufficiently exhibitcharacteristics such as the natural glossiness of a metal in therecorded matter produced using the ultraviolet-curable composition.

Here, in the invention, unless otherwise stated, the viscosity refers toa value which is measured on the basis of JIS 28803 using a rotationalviscometer (for example, manufactured by Anton Paar Japan K.K., PhysicaMCR-301 or the like). In addition, in the present specification,treatment or measurement for which the temperature is not particularlyspecified is performed at 25° C.

As described above, in the invention, it is sufficient if therelationship of η2−η1≤3 is satisfied; however, it is preferable tosatisfy a relationship of η2−η1≤2, and it is more preferable to satisfya relationship of η2−η1≤0.5.

Due to this, the effects as described above are more remarkablyexhibited.

In addition, in the ultraviolet-curable composition of the invention,the viscosity η0 in a state (a default state) before shearing stress isadded at a shearing speed of 1000 sec⁻¹ is preferably 4 mPa·s to 25mPa·s, and more preferably 5 mPa·s to 20 mPa·s.

Due to this, it is possible to make the discharge stability of theultraviolet-curable composition with an ink jet method particularlyexcellent. In addition, it is possible to more effectively prevent theultraviolet-curable composition from being repelled, being excessivelywet and spread, or the like on the recording medium.

In addition, the difference (η1−η0) between the viscosity η1 [Pa·s]described above (the viscosity η1 [mPa·s] at a shearing speed 1000sec⁻¹) and the viscosity η0 [Pa·s] in a state (a default state) beforeshearing stress is added at a shearing speed of 1000 sec⁻¹ is preferably1.5 mPa·s or less, and more preferably 0.5 mPa·s or less.

For η0 before shearing stress is added, it is possible to use a resultwhich is measured beforehand by a vibration-type viscometer or the likein which large shearing stress is not added.

Due to this, it is possible to make the discharge stability of theultraviolet-curable composition with an ink jet method particularlyexcellent and it is possible to make the productivity and reliability ofthe recorded matter particularly excellent.

In addition, it is preferable that the viscosity η1 [mPa·s] describedabove (the viscosity η1 [mPa·s] at a shearing speed 1000 sec⁻¹) and theviscosity η0 [mPa·s] in a state (a default state) before shearing stressis added at a shearing speed of 1000 sec⁻¹ satisfy a relationship ofη1/η0≤1.2, and a relationship of η1/η0≤1.1 is more preferably satisfied.

Due to this, it is possible to make the discharge stability of theultraviolet-curable composition with an ink jet method particularlyexcellent and it is possible to make the productivity and reliability ofthe recorded matter particularly excellent.

Metal Powder

The ultraviolet-curable composition of the invention includes a metalpowder.

Regarding the constituent particles of the metal powder, it issufficient if a site (for example, the vicinity of a surface) which isseen externally is at least formed of a metal material and, for example,the entirety may be formed of a metal material, or there may be a baseportion which is formed of a non-metal material and a coated film whichis formed of a metal material which covers the base portion. Inaddition, a surface treatment layer may be provided by a surfacetreatment agent with respect to base particles where a region whichincludes at least the vicinity of the surface is formed of the metalmaterial.

In addition, it is possible to use a single metal, various types ofalloys, or the like as the metal material which forms the constituentparticles of the metal powder; however, the metal material is preferablymainly formed of Al.

Al is a material with a low specific gravity (2.70 g/cm²) compared toiron or the like and it is possible to make the sedimentation speed ofthe metal powder in the ultraviolet-curable composition particularlyslow, and to make the storage stability of the ultraviolet-curablecomposition particularly excellent.

In addition, it is possible to make the glossiness and sense of luxuryof the recorded matter particularly excellent while suppressingincreases in the production cost of the recorded matter. In addition, Alnaturally has particularly excellent glossiness among various types ofmetal materials; however, the present inventors discovered that theproblem of decreases or the like in the discharge stability with an inkjet method occurs particularly easily in a case of trying to applyparticles which are formed of Al to the ultraviolet-curable composition.In contrast, in the invention, it is possible to reliably prevent theoccurrence of the problem described above even in a case of usingparticles which are formed of Al. That is, the effects of the inventionare more remarkably exhibited in a case where the metal material whichforms the metal powder is mainly formed of Al.

The metal powder may be produced by any method; however, it ispreferably obtained by forming a film which is formed of a metalmaterial by a vapor phase film-forming method and then grinding thefilm. Due to this, it is possible to effectively express the naturalglossiness or the like of the metal material in a pattern (a printedportion) which is formed using the ultraviolet-curable composition ofthe invention. In addition, it is possible to suppress variations in thecharacteristics between each of the particles. In addition, it is evenpossible to favorably produce a comparatively thin metal powder usingthis method.

In a case of producing a metal powder using this method, for example, itis possible to favorably produce the metal powder by forming(film-forming) a film which is formed of a metal material on asubstrate. It is possible to use, for example, a plastic film such aspolyethylene terephthalate or the like as the substrate. In addition,the substrate may have a releasing agent layer on the film-formingsurface.

In addition, the grinding is preferably performed by applying ultrasonicvibration to the film in a liquid. Due to this, it is possible to easilyand reliably obtain a metal powder with the particle diameter which willbe described below and to suppress the generation of variations in thesize, shape, and characteristics between each of the particles.

In addition, as the liquid in a case of grinding with the above method,it is possible to suitably use alcohols such as methanol, ethanol,propanol, and butanol, hydrocarbon-based compounds such as n-heptane,n-octane, decane, dodecane, tetradecane, toluene, xylene, cymene,durene, indene, dipentene, tetrahydronaphthalene, decahydronaphthalene,and cyclohexylbenzene, ether-based compounds such as ethylene glycoldimethyl ether, ethylene glycol diethyl ether, ethylene glycol methylethyl ether, diethylene glycol dimethyl ether, diethylene glycol diethylether, diethylene glycol methyl ethyl ether, diethylene glycol monobutylether acetate, diethylene glycol n-butyl ether, tripropylene glycoldimethyl ether, triethylene glycol diethyl ether, 1,2-dimethoxyethane,bis(2-methoxyethyl) ether, and p-dioxane, and polar compounds such aspropylene carbonate, γ-butyrolactone, N-methyl-2-pyrrolidone,N,N-dimethylformamide (DMF), N,N-dimethylacetamide (DMA), dimethylsulfoxide, cyclohexanone, and acetonitrile. Using the liquid makes itpossible to make the productivity of the metal powder particularlyexcellent while preventing unwanted oxidization or the like of the metalpowder and also to make the variations in the size, shape, andcharacteristics between each of the particles particularly small.

Description will be given below of a case where the constituentparticles of the metal powder are particles where base particles (baseparticles where a region which includes at least the vicinity of thesurface is formed of a metal material) are subjected to a surfacetreatment by a surface treatment agent.

The surface treatment agent has a function of increasing the dispersionstability of the metal powder (particles) in the ultraviolet-curablecomposition.

In addition, as long as surface treatment is carried out such thatsurface energy of the metal powder is decreased, even in a case of usinga polymerizable compound with a low surface tension as the constituentmaterial of the ultraviolet-curable composition, it is possible toreliably more favorably array (carry out leafing) the metal powder inthe vicinity of the outer surface of the printed portion in the recordedmatter produced using the ultraviolet-curable composition and to moreeffectively exhibit characteristics such as the natural glossiness ofthe metal material which forms the metal powder. Therefore, the range ofthe options for the polymerizable compound widens and it is possible toeasily adjust the characteristics of the ultraviolet-curable compositionor the characteristics of the recorded matter produced using theultraviolet-curable composition (for example, the viscosity and thestorage stability of the ultraviolet-curable composition, the abrasionresistance of the recorded matter, or the like) without sacrificing thenatural glossiness of the metal material. On the other hand, the problemthat discharge failures are easily generated with the ink jet methodoccurs remarkably when the constituent particles of the metal powder aresubjected to a surface treatment by a surface treatment agent; however,in the invention, it is possible to stably discharge theultraviolet-curable composition with an ink jet method over a longperiod even in a case where the constituent particles of the metalpowder are subjected to a surface treatment by a surface treatmentagent. That is, the effects of the invention are more remarkablyexhibited in a case where the constituent particles of the metal powderare subjected to a surface treatment by a surface treatment agent.

As the surface treatment agent, it is possible to use, for example, ashort chain compound which has an alkyl group which may have asubstituent group with 2 to 4 carbon atoms, a long chain compound whichhas an alkyl group which may have a substituent group with 8 to 20carbon atoms, a silane compound, a phosphate compound, a carboxylic acidcompound, an isocyanate compound, and the like.

In a case where the alkyl group of the short chain compound and/or thealkyl group of the long chain compound has a substituent group, examplesof the substituent group include a halogen group such as a fluoro group,a chloro group, or a bromo group, a hydroxyl group, and the like.

As a silane compound, it is possible to use a compound which has astructure in which hydrogen atoms and/or hydrocarbon groups (includingones in which some or all of the hydrogen atoms are substituted by otheratoms or an atomic group) are directly bonded to silicon atoms.

In more detail, as the silane compound, it is possible to use, forexample, silicon hydride (Si_(n)H_(2n+2) (here, n is an integer of 1 ormore)), H_(a)SiR_((4−a)) (here, R is a hydrocarbon group which may havea substituent group and a is an integer of 1 to 4), and the like.

As a phosphate compound, it is possible to use, for example, a compound(a long chain alkyl-based phosphate compound) which has at least onealkyl group with 6 or more carbon atoms in a molecule.

In particular, the phosphate compound (a long chain alkyl-basedphosphate compound) preferably has a chemical structure which isrepresented by Formula (1) described below.

POR_(n)(OH)_(3−n)   (1)

(in formula (1), R is CH₃(CH₂)_(m)—, CH₃(CH₂)_(m)(CH₂O)₁—,CH₃(CH₂)_(m)(CH₂CH₂O)₁—, or CH₃(CH₂)_(m)O—, n is an integer of 1 to 3, mis an integer of 5 to 19, and 1 is an integer of 2 to 20).

Due to this, it is possible to make the storage stability of theultraviolet-curable composition particularly excellent and to make theglossiness and abrasion resistance of the printed portion of therecorded matter produced using the ultraviolet-curable compositionparticularly excellent.

In Formula (1), m is preferably an integer of 5 to 19, and morepreferably an integer of 7 to 17. Due to this, the effects as describedabove are more remarkably exhibited.

In addition, in Formula (1), 1 is preferably an integer of 2 to 20, andmore preferably an integer of 4 to 16. Due to this, the effects asdescribed above are more remarkably exhibited.

As a carboxylic acid, it is possible to use a compound (fatty acid)which has a hydrocarbon group and a carboxyl group. Specific examples ofthe compound include decanoic acid, tetradecanoic acid, octadecanoicacid, cis-9-octadecenoic acid, and the like.

As an isocyanate compound, it is possible to use a compound which has apartial structure which is represented by —N═C═O. The compound modifiesa surface of the particles (the base particles) as a compound which hasa partial structure which is represented by —NHCOO— by reacting with themetal material which forms the metal powder (base particles); however,the force of a hydrogen bond acts in the partial structure which isrepresented by —NHCOO—. For this reason, it is possible to carry outfine surface treatment on the surfaces of the particles and toremarkably exhibit the effects as described above.

As an isocyanate compound, it is possible to use a compound which has atleast one isocyanate group in a molecule.

As the isocyanate compound, it is possible to use, for example, acompound which has a chemical structure which is represented by Formula(2) described below.

RNCO   (2)

(in Formula (2), R is CH₃(CH₂)_(m)— and m is an integer of 2 to 18).

In Formula (2), m is preferably an integer of 3 to 14 and morepreferably an integer of 4 to 12.

For example, a fluorine-based compound (a fluorine-based surfacetreatment agent) may be used as a surface treatment agent.

Due to this, it is possible to make the dispersion stability andchemical stability of the metal powder in the ultraviolet-curablecomposition particularly excellent and to make the storage stability ofthe ultraviolet-curable composition particularly excellent. In addition,in the recorded matter produced using the ultraviolet-curablecomposition, it is possible to favorably arrange the metal powder (metalpowder which is subjected to a surface treatment by a fluorine-basedsurface treatment agent) in the vicinity of the outer surface of theprinted portion and to more effectively exhibit characteristics such asthe natural glossiness of the metal material which forms the metalpowder. In addition, it is possible to make the abrasion resistance of aprinted portion of the recorded matter particularly excellent and tomore effectively prevent changes in appearance due to friction (forexample, a decrease in the glossiness, a decrease in aesthetics(aesthetic appearance), and the like). In addition, by the particleswhich form the metal powder being subjected to a surface treatment by afluorine-based surface treatment agent, even in a case of using apolymerizable compound with a low surface tension as a constituentmaterial of the ultraviolet-curable composition, it is possible to morefavorably array (carry out leafing) the metal powder in the vicinity ofthe outer surface of the printed portion in the recorded matter producedusing the ultraviolet-curable composition and to more effectivelyexhibit characteristics such as the natural glossiness of the metalmaterial which forms the metal powder. Accordingly, the range of theoptions for the polymerizable compound widens and it is possible toeasily adjust the characteristics of the ultraviolet-curable compositionor the characteristics of the recorded matter produced using theultraviolet-curable composition (for example, the viscosity and thestorage stability of the ultraviolet-curable composition, the abrasionresistance of the recorded matter, or the like) without sacrificing thenatural glossiness of the metal material.

The fluorine-based compound (the fluorine-based surface treatment agent)preferably has a perfluoro alkyl structure.

Due to this, it is possible to make the storage stability of theultraviolet-curable composition superior and to make the glossiness andabrasion resistance of the printed portion of the recorded matterproduced using the ultraviolet-curable composition superior.

In addition, it is sufficient if the fluorine-based compound (thefluorine-based surface treatment agent) includes at least one fluorineatom in a molecule and more specific examples thereof include a compound(a fluorine-based short chain compound, a fluorine-based long chaincompound, a fluorine-based silane compound, a fluorine-based phosphatecompound, a fluorine-substituted fatty acid, a fluorine-based isocyanatecompound, and the like) which has a structure in which at least some ofthe hydrogen atoms of the short chain compound, the long chain compound,the silane compound, the phosphate compound, the carboxylic acid, andthe isocyanate compound described above are substituted by fluorineatoms or the like.

The effects as described above are more remarkably exhibited by usingthese compounds as the surface treatment agent. In particular, it ispossible to more effectively decrease the surface free energy of theconstituent particles of the metal powder, the difference of theinterface energy with a polymerizable compound is made larger and thehydrophobic interaction acts more strongly, and it is possible to moreeffectively array the metal powder on the surface of the recordedmatter. As the result, it is possible to make the glossiness of therecorded matter particularly excellent.

Among these, in a case of using the fluorine-based silane compound, therecorded matter produced using the ultraviolet-curable compositionexhibits particularly excellent durability and weather resistance and itis possible to maintain the hardness of the film over a longer period.

In addition, since the phosphate compound surface treatment agent isstrong against acid, in a case of using a fluorine-based phosphatecompound, the recorded matter produced using the ultraviolet-curablecomposition exhibits excellent durability and weather resistance evenunder an acidic environment.

In addition, in a case of using a fluorine-substituted fatty acid (afluorine-based fatty acid), it is possible to more effectively performthe surface treatment with respect to the base particles which areformed of noble metals such as gold, silver, and platinum, copper,aluminum, and the like and, since it is possible to form a film (asurface treatment layer) of which a functional group is small and thecrystallinity is high, it is possible to effectively decrease thesurface free energy. As the result, it is possible to effectively lineup smaller particles on the surface of the recorded matter and tofurther improve the abrasion resistance.

In addition, in a case of using a fluorine-based isocyanate compound,since it is possible to carry out a finer surface treatment with respectto the base particles and to strengthen the bonding force with the baseparticles and, the durability of the metal powder is increased, it ispossible to maintain the abrasion resistance over a longer period.

The fluorine-based silane compound preferably has the chemical structurewhich is represented by Formula (3) described below.

R¹SiX_(a) ¹R_((3−a)) ²   (3)

(in Formula (3), R¹ represents a hydrocarbon group in which some or allof the hydrogen atoms are substituted by fluorine atoms, X¹ represents ahydrolyzable group, an ether group, a chloro group, or a hydroxyl group,R² represents an alkyl group with 1 to 4 carbon atoms, and a is aninteger of 1 to 3).

Due to this, it is possible to make the storage stability of theultraviolet-curable composition particularly excellent and to make theglossiness and abrasion resistance of the printed portion of therecorded matter produced using the ultraviolet-curable compositionparticularly excellent.

Examples of R¹ in formula (3) include an alkyl group, an alkenyl group,an aryl group, an aralkyl group and the like in which some or all of thehydrogen atoms of these groups are substituted with fluorine atoms,furthermore, at least a part of the hydrogen atoms included in themolecular structure (hydrogen atoms which are not substituted withfluorine atoms) may be substituted with an amino group, a carboxylgroup, a hydroxyl group, a thiol group, or the like, or an aromatic ringsuch as a heteroatom such as —O—, —S—, —NH—, or —N═ or benzene may beincluded in the carbon chain. Specific examples of R¹ include a phenylgroup, a benzyl group, a phenethyl group, a hydroxyphenyl group, achlorophenyl group, an amino phenyl group, a naphthyl group, ananthranilic group, a pyrenyl group, a thienyl group, a pyrrolyl group, acyclohexyl group, a cyclohexenyl group, a cyclopentyl group, acyclopentenyl group, a pyridinyl group, a methyl group, an ethyl group,a n-propyl group, an isopropyl group, a n-butyl group, an isobutylgroup, a sec-butyl group, a tert-butyl group, an octadecyl group, an-octyl group, a chloromethyl group, a methoxyethyl group, ahydroxyethyl group, an amino ethyl group, a cyano group, amercaptopropyl group, a vinyl group, an allyl group, an acryloxyethylgroup, a methacryloxy ethyl group, a glycidoxypropyl group, an acetoxygroup, and the like in which some or all of the hydrogen atoms of thesegroups are substituted with fluorine atoms.

Examples of the fluorine-based silane compound which has a perfluoroalkyl structure (C_(n)F_(2n+1)) include the compound represented byFormula (4) below.

C_(n)F_(2n+1)(CH₂)_(m)SiX_(a) ¹R_((3−a)) ²   (4)

(in Formula (4), X¹ represents a hydrolyzable group, an ether group, achloro group, or a hydroxyl group, R² represents an alkyl group with 1to 4 carbon atoms, n is an integer of 1 to 14, m is an integer of 2 to6, and a is an integer of 1 to 3).

Specific examples of the compound which has the structure includeCF₃—CH₂CH₂—Si(OCH₃)₃, CF₃(CF₂)₃—CH₂CH₂—Si(OCH₃)₃,CF₃(CF₂)₅—CH₂CH₂—Si(OCH₃)₃, CF₃(CF₂)₅—CH₂CH₂—Si(OC₂H₅)₃,CF₃(CF₂)₇—CH₂CH₂—Si(OCH₃)₃, CF₃(CF₂)₁₁—CH₂CH₂—Si(OC₂H₅)₃,CF₃(CF₂)₃—CH₂CH₂—Si(CH₃)(OCH₃)₂, CF₃(CF₂)₇—CH₂CH₂—Si(CH₃)(OCH₃)₂,CF₃(CF₂)₈—CH₂CH₂—Si(CH₃)(OC₂H₅)₂, CF₃(CF₂)₈—CH₂CH₂—Si(C₂H₅)(OC₂H₅)₂, andthe like.

In addition, as the fluorine-based silane compound, it is also possibleto use a compound which has a perfluoro alkyl ether structure(C_(n)F_(2n+1)O) instead of the perfluoro alkyl structure(C_(n)F_(2n+1)) described above.

Examples of the fluorine-based silane compound which has a perfluoroalkyl ether structure (C_(n)F_(2n+1)O) include the compound representedby Formula (5).

C_(p)F_(2p+1)O(C_(p)F_(2p)O)_(r)(CH₂)_(m)SiX_(a) ¹R_((3−a)) ²   (5)

(in Formula (5), X¹ represents a hydrolyzable group, an ether group, achloro group, or a hydroxyl group, R² represents an alkyl group with 1to 4 carbon atoms, p is an integer of 1 to 4, r is an integer of 1 to10, m is an integer of 2 to 6, and a is an integer of 1 to 3).

Specific examples of the compound having such a structure includeCF₃O(CF₂O)₆—CH₂CH₂—Si(OC₂H₅)₃, CF₃O(C₃F₆O)₄—CH₂CH₂—Si(OCH₃)₃,CF₃O(C₃F₆O)₂(CF₂O)₃—CH₂CH₂—Si(OCH₃)₃, CF₃O(C₃F₆O)₈—CH₂CH₂—Si(OCH₃)₃,CF₃O(C₄F₉O)₅—CH₂CH₂—Si(OCH₃)₃, CF₃O(C₄F₉O)₅—CH₂CH₂—Si(CH₃)(OC₂H₅)₂,CF₃O(C₃F₆O)₄—CH₂CH₂—Si(C₂H₅)(OCH₃)₂, and the like.

As the fluorine-based phosphate compound, it is possible to use aphosphate compound which has at least one fluorine atom in the molecule.

In particular, the fluorine-based phosphate compound preferably has thechemical structure which is represented by Formula (6) described below.

POR_(n)(OH)3_(−n)   (6)

(in formula (6), R is CF₃(CF₂)_(m)—, CF₃(CF₂)_(m)(CH₂)₁—,CF₃(CF₂)_(m)(CH₂O)₁—, CF₃(CF₂)_(m)(CH₂CH₂O)₁—, CF₃(CF₂)_(m)O—, or,CF₃(CF₂)_(m)(CH₂)₁O—, n is an integer of 1 to 3, m is an integer of 2 to18, and 1 is an integer of 1 to 18).

Due to this, it is possible to make the storage stability of theultraviolet-curable composition particularly excellent and to make theglossiness and abrasion resistance of the printed portion of therecorded matter produced using the ultraviolet-curable compositionparticularly excellent.

In Formula (6), m is preferably an integer of 3 to 14, and morepreferably an integer of 4 to 12. Due to this, the effects as describedabove are more remarkably exhibited.

In addition, in Formula (6), 1 is preferably an integer of 1 to 14, andmore preferably an integer of 1 to 10. Due to this, the effects asdescribed above are more remarkably exhibited.

As the fluorine-substituted fatty acid (the fluorine-based fatty acid),it is possible to use a fatty acid which has at least one fluorine atomin the molecule.

Examples of the fluorine-substituted fatty acid include CF₃—CH₂CH₂—COOH,CF₃(CF₂)₃—CH₂CH₂—COOH, CF₃(CF₂)₅—CH₂CH₂—COOH, CF₃(CF₂)₆—CH₂CH₂—COOH,CF₃(CF₂)₇—CH₂CH₂—COOH, CF₃(CF₂)₉—CH₂CH₂—COOH, and esters thereof and thelike, among them, CF₃(CF₂)₅—CH₂CH₂—COOH is preferable.

Due to this, since it is possible to make a stronger bond with siliconor the metal atoms such as aluminum, magnesium, and titanium which formthe base particles by a dehydration reaction due to heating and to forma fine film, it is possible to effectively decrease the surface energyof the particles.

As the fluorine-based isocyanate compound, it is possible to use acompound which has at least one fluorine atom and at least oneisocyanate group in a molecule.

As the fluorine-based isocyanate compound, it is possible to use acompound which has the chemical structure which is represented byFormula (7) described below.

RfNCO   (7)

(in Formula (7), Rf is CF₃(CF₂)_(m)— or CF₃(CF₂)_(m)(CH₂)₁—, m is aninteger of 2 to 18, and 1 is an integer of 1 to 18).

Due to this, it is possible to make the storage stability of theultraviolet-curable composition particularly excellent. In addition, inthe recorded matter produced using the ultraviolet-curable composition,it is possible to more favorably array (carry out leafing) the metalpowder in the vicinity of the outer surface of the printed portion tomake the glossiness of the printed portion of the produced recordedmatter particularly excellent. In addition, it is possible to make theabrasion resistance of the printed portion of the produced recordedmatter particularly excellent.

In Formula (7), m is preferably an integer of 3 to 14 and morepreferably an integer of 4 to 12. Due to this, the effects as describedabove are more remarkably exhibited.

In addition, in Formula (7), 1 is preferably an integer of 1 to 14 andmore preferably an integer of 1 to 10. Due to this, the effects asdescribed above are more remarkably exhibited.

In addition, the metal powder may be subjected to a surface treatment bya plurality of types of surface treatment agents. In this case, thesurface treatment by a plurality of types of surface treatment agentsmay be carried out on the same particles or the metal powder may includea plurality of types of particles subjected to a surface treatment bydifferent surface treatment agents.

The surface treatment agent described above may directly treat the baseparticles; however, the treatment by the surface treatment agent ispreferably performed with respect to the base particles after the baseparticles are processed with an acid or a base. Due to this, it ispossible to more reliably carry out modification by chemical bondingwith the base particle surface using the surface treatment agent and tomore effectively exhibit the effects as described above. As an acid, itis possible to use, for example, proton acids such as hydrochloric acid,sulfuric acid, phosphoric acid, nitric acid, acetic acid, carbonic acid,formic acid, benzoic acid, chlorous acid, hypochlorous acid, sulfurousacid, hyposulfurous acid, nitrous acid, hyponitrous acid, phosphorousacid, and hypophosphorous acid. Among these, hydrochloric acid,phosphoric acid, and acetic acid are favorable. On the other hand, as abase, it is possible to use, for example, sodium hydroxide, potassiumhydroxide, calcium hydroxide, and the like. Among these, sodiumhydroxide and potassium hydroxide are favorable.

In a case of carrying out a plurality of types of surface treatments onthe same particles, the surface treatments may be performed by beingdivided into a plurality of steps which correspond to each of thesurface treatment agents or the surface treatments may be performed inthe same step by a plurality of types of surface treatment agents.

In addition, for example, the surface treatment of the base particlesusing the surface treatment agent may be performed by including thesurface treatment agent in a liquid when grinding a film made of a metalformed by the vapor phase film-forming method in a liquid to form thebase particles as described above.

Due to this, it is possible to advance the surface treatment along withthe forming of the base particles of which the size uniformity isexcellent, it is possible to quickly perform the surface treatment on aclean surface which is exposed due to the grinding, and it is possibleto make the quality and productivity of the metal powder and theultraviolet-curable composition particularly excellent. In addition, itis possible to carry out the surface treatment on each site of the metalpowder with high uniformity. In addition, in a case of using the agentsdescribed above as the surface treatment agent (particularly in a caseof using a fluorine-based phosphate compound), by the aggregation of thebase particles subjected to the surface treatment being appropriatelyinhibited, the fluidity of the liquid in which the base particles aredispersed is increased, it is possible to more effectively grind thefilm, it is possible to more efficiently obtain a metal powder whichsatisfies the particle diameter conditions which will be describedbelow, and it is possible to make the quality and productivity of themetal powder and the ultraviolet-curable composition superior.

In a case of carrying out a plurality of types of surface treatments onthe same particles, the surface treatments may be performed by beingdivided into a plurality of steps which correspond to each of thesurface treatment agents or the surface treatments may be performed inthe same step by a plurality of types of surface treatment agents.

The particles which form the metal powder may take any shape such as asphere, a spindle, or a needle, and are preferably flaky.

Due to this, it is possible to arrange the metal powder such that themain surfaces of the particles are along the surface shape of therecording medium on the recording medium to which theultraviolet-curable composition is added, it is possible to effectivelyexhibit the natural glossiness or the like of the metal material whichforms the metal powder even in the obtained recorded matter, and it ispossible to make the glossiness and sense of luxury of the formedpattern (a printed portion) particularly excellent. In addition, in acase where the metal powder is subjected to the surface treatmentdescribed above, it is possible to make the abrasion resistance of therecorded matter particularly excellent. In addition, the problem in thebackground art that the discharge stability with an ink jet methoddecreases occurs particularly remarkably in a case of using a metalpowder which includes flaky particles; however, in the invention, it ispossible to effectively prevent the occurrence of the problem describedabove even when the particles which form the metal powder are flaky.That is, the effects of the invention are more remarkably exhibited in acase where the particles which form the metal powder are flaky.

In the invention, flaky refers to a shape of which an area when observedfrom a predetermined angle (when viewed in plan) is larger than an areawhen observed from an angle which is orthogonal with the observingdirection as a flat shape, a curved plane, or the like, and, inparticular, the ratio (S₁/S₀) with respect to an area S₁ [μm²] whenobserved (when viewed in plan view) from a direction in which theprojection area is the maximum and an area S₀ [μm²] when observed from adirection in which an area when observed in the direction whichorthogonal to the observing direction is the maximum is preferably 2 ormore, more preferably 5 or more, and even more preferably 8 or more. Asthe value, it is possible to, for example, adopt the average value ofthe calculated values for any 10 arbitrary particles by observing theparticles.

In a case where the particles which form the metal powder are flaky, theaverage thickness of the particles is preferably 10 nm to 80 nm, andmore preferably 20 nm to 70 nm.

For example, the ratio (S₁/S₀) and the thickness can be observed using atransmission electron microscope and a scanning electron microscope, andspecific examples include a transmission electron microscope (TEM, JOELJEM-2000EX), a field emission scanning electron microscope (FE-SEM,Hitachi S-4700), a scanning transmission electron microscope (STEM,“HD-2000” manufactured by Hitachi High-Technologies Corporation) and thelike. The thickness means an average thickness and is an average valueobtained such that the measurement is performed 10 times.

Due to this, the effects due to the particles described above beingflaky are more remarkably exhibited.

The average particle diameter (D₅₀) of the metal powder is preferably200 nm to 3.0 μm, more preferably 250 nm to 640 nm, and even morepreferably 300 nm to 600 nm.

Due to this, it is possible to make the glossiness and sense of luxuryof the recorded matter produced using the ultraviolet-curablecomposition particularly excellent. In addition, it is possible to makethe storage stability and discharge stability of the ultraviolet-curablecomposition superior.

Here, in the invention, the average particle diameter refers to themedian diameter of volume distribution where the particle dispersingliquid is measured using a laser diffraction scattering method and, in acase where a large number of measurement results are represented as theaccumulation of the presence ratios for each size (particle diameter),the average particle diameter is the size (the volume average particlediameter) of the particles which exhibits exactly 50% of the centralvalue in the accumulation. Examples of the measurement device include alaser diffraction scattering particle size analyzer, Microtrack MT-3000(manufactured by Nikkiso Co., Ltd.). The volume average particlediameters (D50) in the below-described Examples are values measured bythe above-described Microtrack MT-3000.

The particle diameter (D₁₀) at a volume accumulation distribution ratioof 10% from the fine particle side of the metal powder is preferably 100nm to 1.1 μm, more preferably 150 nm to 400 nm, and even more preferably180 nm to 350 nm.

Due to this, it is possible to make the particle distribution of themetal powder sharper and to make the discharge stability of theultraviolet-curable composition with an ink jet method particularlyexcellent.

The particle diameter (D₉₀) at a volume accumulation distribution ratioof 90% from the fine particle side of the metal powder is preferably 300nm to 4.0 μm, more preferably 400 nm to 1300 nm, and even morepreferably 500 nm to 1100 nm.

Due to this, it is possible to make the particle distribution of themetal powder sharper and to make the discharge stability of theultraviolet-curable composition with an ink jet method particularlyexcellent.

The half-value width in the particle distribution of the metal powder(the distance between D25 and D75) is preferably 0.50 μm or less, morepreferably 0.45 μm or less, and even more preferably 0.30 μm or less.

Due to this, it is possible to make the particle distribution of themetal powder sharper and to make the discharge stability of theultraviolet-curable composition with an ink jet method particularlyexcellent.

The content ratio of the metal powder in the ultraviolet-curablecomposition is preferably 0.9 mass % to 29 mass %, and more preferably1.2 mass % to 19.3 mass %.

Due to this, it is possible to satisfy both the glossiness and theabrasion resistance of the printed portion which is formed using theultraviolet-curable composition at a higher level. In addition, it ispossible to make the storage stability of the ultraviolet-curablecomposition and the discharge stability of the ultraviolet-curablecomposition with an ink jet method particularly excellent.

Polymerizable Compound

The polymerizable compound is a component which is polymerized by beingirradiated with ultraviolet rays to be cured. Including the componentmakes it possible to make the abrasion resistance, water resistance,solvent resistance, and the like of the recorded matter produced usingthe ultraviolet-curable composition excellent.

The polymerizable compound is in liquid form and preferably functions asa dispersing medium which disperses the metal powder in theultraviolet-curable composition.

Due to this, since it is not necessary to separately use a dispersingmedium which is removed (evaporated) in the process of producing therecorded matter and it is not necessary to provide a step of removingthe dispersing medium even when producing the recorded matter, it ispossible to make the productivity of the recorded matter particularlyexcellent. In addition, since it is not necessary to use a dispersingmedium which is generally used as an organic solvent, it is possible toprevent the occurrence of the problem of volatile organic compounds(VOC). In addition, by including a polymerizable compound, it ispossible to make the adhesiveness of the printed portion which is formedusing the ultraviolet-curable composition with respect to various typesof recording media (substrates) excellent. That is, by including apolymerizable compound, the ultraviolet-curable composition is excellentin terms of corresponding to the media.

It is sufficient if the polymerizable compound is a component which ispolymerized by being irradiated with ultraviolet rays, and it ispossible to use, for example, various types of monomers, various typesof oligomers (which include dimers, trimers, and the like), and thelike; however, the ultraviolet-curable composition preferably includesat least a monomer component as a polymerizable compound. Since amonomer is generally a component with low viscosity compared to anoligomer component or the like, it is advantageous in terms of makingthe discharge stability or the like of the ultraviolet-curablecomposition particularly excellent.

In particular, the ultraviolet-curable composition preferably includes amonomer which has an alicyclic structure as a polymerizable compound.

By including a monomer which has an alicyclic structure along with thethixotropy suppressing agent, it is possible to make the storagestability and discharge stability of the ultraviolet-curable compositionparticularly excellent and it is also possible to make the glossinessand abrasion resistance of the printed portion of the recorded matterproduced using the ultraviolet-curable composition particularlyexcellent.

Examples of the monomer having an alicyclic structure includetris(2-(meth)acryloyloxyethyl) isocyanurate, dicyclopentenyloxyethyl(meth) acrylate, adamantyl (meth)acrylate, γ-butyrolactone(meth)acrylate, N-vinylcaprolactam, N-vinylpyrrolidone,pentamethylpiperidyl (meth)acrylate, tetramethyl piperidyl(meth)acrylate, 2-methyl-2-adamantyl (meth) acrylate,2-ethyl-2-adamantyl (meth)acrylate, mevalonic lactone (meth)acrylate,dimethylol tricyclodecane di(meth)acrylate, dimethylol dicyclopentanedi(meth)acrylate, dicyclopentenyl (meth) acrylate, dicyclopentanyl(meth) acrylate, isobornyl (meth) acrylate, cyclohexyl (meth) acrylate,(meth) acryloylmorpholine, tetrahydrofurfuryl (meth)acrylate, phenylglycidyl ether (meth)acrylate, EO-modified hydrogenated bisphenol Adi(meth)acrylate, di(meth)acrylated isocyanurate, tri(meth)acrylatedisocyanurate and the like, and preferably include one type or two ormore types selected from a group formed of tris(2-acryloyloxyethyl)isocyanurate, dicyclopentenyloxy ethyl acrylate, adamantyl acrylate,γ-butyrolactone acrylate, N-vinylcaprolactam, N-vinylpyrrolidone,pentamethylpiperidyl acrylate, tetramethyl piperidyl acrylate,2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl acrylate, mevaloniclactone acrylate, dimethylol tricyclodecane diacrylate, dimethyloldicyclopentane diacrylate, dicyclopentenyl acrylate, dicyclopentanylacrylate, isobornyl acrylate, cyclohexyl acrylate, acryloylmorpholine,tetrahydrofurfuryl acrylate, cyclohexane spiro-2-(1,3-dioxolan-4-yl)methyl acrylate, and (2-methyl-2-ethyl-1,3-dioxolan-4-yl) methylacrylate.

Due to this, it is possible to make the glossiness and sense of luxuryof the recorded matter produced using the ultraviolet-curablecomposition superior. In addition, by including the monomer along with athixotropy suppressing agent, it is possible to make the storagestability and discharge stability of the ultraviolet-curable compositionsuperior.

Among these, in a case of including one type or two or more typesselected from a group formed of acryloylmorpholine, tetrahydrofurfurylacrylate, γ-butyrolactone acrylate, N-vinylcaprolactam, andN-vinylpyrrolidone, it is possible to make the dispersion stability ofthe metal powder in the ultraviolet-curable composition superior, it isalso possible to more favorably array the metal powder in the vicinityof the outer surface of the printed portion in the recorded matterproduced using the ultraviolet-curable composition, and it is possibleto make the glossiness of the obtained recorded matter superior. Inaddition, by including the monomer along with a thixotropy suppressingagent, it is possible to make the discharge stability of theultraviolet-curable composition superior.

In addition, from the point of view of the curing speed of theultraviolet-curable composition when irradiated with ultraviolet raysand further improvement of the productivity of the recorded matter, itis preferable to include one type or two or more types selected from agroup formed of tris(2-acryloyloxyethyl) isocyanurate,dicyclopentenyloxyethyl acrylate, γ-butyrolactone acrylate,N-vinylpyrrolidone, dimethylol tricyclodecane diacrylate, dimethyloldicyclopentane diacrylate, dicyclopentenyl acrylate, dicyclopentanylacrylate, acryloylmorpholine, and tetrahydrofurfuryl acrylate, and morepreferably, acryloylmorpholine, and/or γ-butyrolactone acrylate, andeven more preferably γ-butyrolactone acrylate.

In addition, in a case of including one type or two or more typesselected from a group formed of cyclohexyl acrylate, tetrahydrofurfurylacrylate, and benzyl acrylate, it is possible to make the flexibility ofthe printed portion which is formed by curing the ultraviolet-curablecomposition superior.

In addition, from the point of view of further improving the abrasionresistance of the printed portion which is formed by curing theultraviolet-curable composition, it is preferable to include one type ortwo or more types selected from a group formed oftris(2-acryloyloxyethyl) isocyanurate, dicyclopentenyloxyethyl acrylate,adamantyl acrylate, γ-butyrolactone acrylate, N-vinylcaprolactam,N-vinylpyrrolidone, dimethylol tricyclodecane diacrylate, dimethyloldicyclopentane diacrylate, dicyclopentenyl acrylate, dicyclopentanylacrylate, isobornyl acrylate, and acryloylmorpholine, and morepreferably γ-butyrolactone acrylate, and/or, N-vinylcaprolactam.

In addition, in a case of including one type or two or more typesselected from a group formed of γ-butyrolactone acrylate,N-vinylcaprolactam, N-vinylpyrrolidone, isobornyl acrylate, andtetrahydrofurfuryl acrylate, it is possible to more effectively preventdecreases in the glossiness or the like due to unwanted creases or thelike being generated in the printed portion, which is formed by curingthe ultraviolet-curable composition, by reducing the contraction ratewhen curing the ultraviolet-curable composition.

The content ratio of the monomer which has an alicyclic structure in theultraviolet-curable composition is preferably 38 mass % to 90 mass %,more preferably 49 mass % to 88 mass %, and even more preferably 54 mass% to 85 mass %.

Due to this, the dispersion stability of the metal powder isparticularly excellent, and excellent discharge stability is obtainedover a long period. Here, the ultraviolet-curable composition mayinclude two or more types of compounds as a monomer which has analicyclic structure. In this case, the total content ratio is preferablya value within these ranges.

Regarding the monomer which has an alicyclic structure, the number ofconstituent atoms in the cyclic structure which is formed by a commonbond is preferably 5 or more and more preferably 6 or more.

Due to this, it is possible to make the storage stability of theultraviolet-curable composition particularly excellent.

As a monomer which has an alicyclic structure, the ultraviolet-curablecomposition preferably includes a monofunctional monomer (amonofunctional monomer which has a hetero ring which does not exhibitaromaticity) which includes a hetero atom in an alicyclic structure.

Due to this, the dispersion stability of the metal powder isparticularly excellent, and excellent discharge stability is obtainedover a long period. Examples of such monofunctional monomers includetris(2-(meth)acryloyloxyethyl) isocyanurate, γ-butyrolactone (meth)acrylate, N-vinylcaprolactam, N-vinylpyrrolidone, pentamethylpiperidyl(meth) acrylate, tetramethyl piperidyl (meth) acrylate, mevaloniclactone (meth)acrylate, (meth)acryloylmorpholine, tetrahydrofurfuryl(meth)acrylate, and the like.

The content ratio of the monofunctional monomer (a monofunctionalmonomer which includes a hetero atom in an alicyclic structure) in theultraviolet-curable composition is preferably 8 mass % to 80 mass % andmore preferably 13 mass % to 75 mass %.

Due to this, it is possible to favorably use the above for producingrecorded matter which is provided with a pattern (a printed portion) inwhich curing contraction is suppressed, there is little scattering, andthe glossiness is superior. Here, the ultraviolet-curable compositionmay include two or more types of compounds as the single functionalmonomer which includes a hetero atom in an alicyclic structure. In thiscase, the total content ratio is preferably a value within these ranges.

In the invention, the polymerizable compound which forms theultraviolet-curable composition may include a monomer which does nothave an alicyclic structure.

Examples of such monomers (monomers which do not have an alicyclicstructure) include phenoxyethyl (meth)acrylate, benzyl (meth)acrylate,2-(2-vinyloxyethoxy) ethyl (meth)acrylate, dipropylene glycoldi(meth)acrylate, tripropylene glycol di(meth)acrylate, 2-hydroxy3-phenoxypropyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate lauryl(meth)acrylate, 2-methoxyethyl (meth)acrylate, isooctyl (meth)acrylate,stearyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate,1H,1H,5H-octafluoropentyl (meth) acrylate, 2-hydroxyethyl(meth)acrylate, 2-hydroxypropyl (meth)acrylate, isobutyl (meth)acrylate,t-butyl (meth)acrylate, ethyl carbitol (meth)acrylate,2,2,2-trifluoroethyl (meth)acrylate, 2,2,3,3-tetrafluoropropyl (meth)acrylate, methoxy triethylene glycol (meth)acrylate, PO-modifiednonylphenol (meth)acrylate, EO-modified nonylphenol (meth)acrylate,EO-modified 2-ethylhexyl (meth)acrylate, phenoxy diethylene glycol(meth)acrylate, EO-modified phenol (meth)acrylate, EO-modified cresol(meth)acrylate, methoxy polyethylene glycol (meth)acrylate, dipropyleneglycol (meth)acrylate, 2-n-butyl-2-ethyl-1,3-propanedioldi(meth)acrylate, tetraethylene glycol di(meth)acrylate, 1,9-nonanedioldi(meth)acrylate, 1,4-butanediol di(meth)acrylate, bisphenol AEO-modified di(meth)acrylate, 1,6-hexanediol di(meth)acrylate,polyethylene glycol 200 di(meth)acrylate, polyethylene glycol 300di(meth)acrylate, neopentyl glycol hydroxypivalate di(meth)acrylate,2-ethyl-2-butyl-propane diol di(meth)acrylate, polyethylene glycol 400di(meth)acrylate, polyethylene glycol 600 di(meth)acrylate,polypropylene glycol di(meth)acrylate, PO-modified bisphenol Adi(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritoltri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate,glycerin PO-added tri(meth)acrylate, tris(meth)acryloyloxyethylphosphate, pentaerythritol tetra(meth)acrylate, PO-modifiedtrimethylolpropane tri(meth)acrylate, 2-(meth)acryloyloxyethylphthalate, 3-(meth)acryloyloxy propyl acrylate, w-carboxy (meth)acryloyloxyethyl phthalate, ditrimethylolpropane tetra (meth) acrylate,dipentaerythritol penta/hexa(meth)acrylate, dipentaerythritolhexa(meth)acrylate, and the like, and preferably include one type or twoor more types selected from a group formed of phenoxyethyl acrylate,benzyl acrylate, 2-(2-vinyloxyethoxy) ethyl acrylate, dipropylene glycoldiacrylate, tripropylene glycol diacrylate, 2-hydroxy 3-phenoxypropylacrylate, and 4-hydroxybutyl acrylate.

Including the monomer which does not have an alicyclic structure inaddition to the monomer which has an alicyclic structure makes thereactivity of the ultraviolet-curable composition after discharging withan ink jet method particularly excellent, while making the storagestability and discharge stability of the ultraviolet-curable compositionexcellent, and it is possible to make the productivity of the recordedmatter particularly excellent and also to make the abrasion resistanceor the like of the formed pattern particularly excellent.

Among these, in a case of including phenoxyethyl acrylate, it ispossible to favorably array the metal powder in the vicinity of theouter surface of the printed portion in the recorded matter producedusing the ultraviolet-curable composition and to make the glossiness ofthe obtained recorded matter superior.

In addition, in a case of including acrylic acid 2-(2-vinyloxyethoxy)ethyl, it is possible to make the curing speed of theultraviolet-curable composition when irradiated with ultraviolet raysand the productivity of the recorded matter superior.

In addition, in a case of including phenoxyethyl acrylate and/or2-hydroxy 3-phenoxypropyl acrylate, it is possible to make theflexibility of the printed portion which is formed by curing theultraviolet-curable composition superior.

In addition, from the point of view of further improving the abrasionresistance of the printed portion which is formed by curing theultraviolet-curable composition, one type or two or more types selectedfrom a group formed of acrylic acid 2-(2-vinyloxyethoxy) ethyl,dipropylene glycol diacrylate, and tripropylene glycol diacrylate arepreferably included, and acrylic acid 2-(2-vinyloxyethoxy) ethyl is morepreferably included.

In addition, in a case of including phenoxyethyl acrylate, it ispossible to more effectively prevent a decrease in the glossiness or thelike due to unwanted creases or the like being generated in the printedportion which is formed by curing the ultraviolet-curable composition bymaking the contraction rate when curing the ultraviolet-curablecomposition smaller.

The content ratio of monomers other than a monomer which has analicyclic structure in the ultraviolet-curable composition is preferably4 mass % to 50 mass %, and more preferably 9 mass % to 40 mass %.

Due to this, the adjustment of the curing speed, flexibility, thecontraction rate when curing, or the like of the ultraviolet-curablecomposition is easier. Here, the ultraviolet-curable composition mayinclude two or more types of compounds as the monomer which does nothave an alicyclic structure. In this case, the total content ratio ispreferably a value within these ranges.

The ultraviolet-curable composition may include an oligomer (whichincludes a dimer, trimer, and the like), a prepolymer, and the likeother than a monomer as a polymerizable compound. It is possible to usean oligomer and a prepolymer, for example, which have the monomer asdescribed above as a constituent component. The ultraviolet-curablecomposition particularly preferably includes a multifunctional oligomer.

Due to this, it is possible to make the abrasion resistance or the likeof a formed pattern particularly excellent while making the storagestability of the ultraviolet-curable composition and the dischargestability with an ink jet method particularly excellent. As an oligomer,a urethane oligomer of which the repeating structure is urethane, anepoxy oligomer of which the repeating structure is epoxy, and the likeare preferably used.

The content ratio of the polymerizable compound in theultraviolet-curable composition is preferably 68 mass % to 99 mass %,and more preferably 79 mass % to 98 mass %.

Due to this, it is possible to make the storage stability, dischargestability, and curability of the ultraviolet-curable compositionsuperior, and also to make the glossiness, abrasion resistance, and thelike of the recorded matter produced using the ultraviolet-curablecomposition superior. Here, the ultraviolet-curable composition mayinclude two or more types of compounds as a polymerizable compound. Inthis case, the total content ratio of the compounds is preferably avalue within these ranges.

Thixotropy Suppressing Agent

The ultraviolet-curable composition of the invention includes athixotropy suppressing agent in addition to the metal powder and thepolymerizable compound.

The thixotropy suppressing agent has a function which suppresses thethixotropy of the ultraviolet-curable composition and suppressesincreases in the viscosity when adding shearing stress.

As the thixotropy suppressing agent, it is possible to use, for example,a phosphoric acid-based dispersing agent (a phosphoric ester-baseddispersing agent), an alkyl amine-based dispersing agent, aurethane-based dispersing agent, an acryl-based dispersing agent, anacrylic silicon-based dispersing agent, fluorine-containing powder, apolycarboxylic acid-based dispersing agent, and the like, and one typeor two or more types selected from a group formed of a phosphoricacid-based dispersing agent, an alkyl amine-based dispersing agent, andfluorine-containing powder are preferably used.

Due to this, the effects due to including the thixotropy suppressingagent are more remarkably exhibited and it is possible to make thedischarge stability of the ultraviolet-curable composition with an inkjet method particularly preferable. In addition, since the thixotropysuppressing agent sufficiently exhibits the effects as described aboveeven when the content ratio is comparatively low, it is possible to makethe content ratio of other components in the ultraviolet-curablecomposition relatively high. As the result, it is possible to make theglossiness, abrasion resistance, and the like of the recorded matterparticularly excellent while making the productivity of the recordedmatter and the reliability of the recorded matter excellent.

In particular, by including a specific dispersing agent as a thixotropysuppressing agent, in addition to the effect of improving the dischargestability by including a thixotropy suppressing agent, it is possible tomake the dispersion stability or the like of the metal powder or thelike in the ultraviolet-curable composition excellent, and to make thestorage stability of the ultraviolet-curable composition particularlyexcellent.

As the phosphoric acid-based dispersing agent (a phosphoric ester-baseddispersing agent) which functions as a thixotropy suppressing agent, itis possible to use, for example, DISPERBYK-118, DISPERBYK-110, andDISPERBYK-102 (produced by BYK Japan K.K.), AQ-330 (produced by KusumotoChemicals, Ltd.), Prisurf A212C and Prisurf A215C (produced by DKS Co.,Ltd.), and the like.

The acid value of the phosphoric acid-based dispersing agent (aphosphoric ester-based dispersing agent) which functions as a thixotropysuppressing agent is not particularly limited, and preferably 15 mgKOH/gto 110 mgKOH/g, and more preferably 20 mgKOH/g to 105 mgKOH/g.

As the amine-based dispersing agent (particularly a high branchedpolyamine-based dispersing agent) which functions as a thixotropysuppressing agent, it is possible to use, for example, DISPERBYK-140(produced by BYK Japan K.K.) and the like.

The acid value of the alkyl amine-based dispersing agent which functionsas a thixotropy suppressing agent is not particularly limited, andpreferably 10 mgKOH/g to 100 mgKOH/g, and more preferably 20 mgKOH/g to80 mgKOH/g.

The amine value of the amine-based dispersing agent which functions as athixotropy suppressing agent is not particularly limited, and preferably40 mgKOH/g to 100 mgKOH/g, and more preferably 50 mgKOH/g to 80 mgKOH/g.

As the urethane-based dispersing agent which functions as a thixotropysuppressing agent, it is possible to use, for example, DISPERBYK-161,162, 163, 167, 168, 182, 183, 184, 185, 2163, and 2164 (the above areall produced by BYK Japan K.K.) and the like.

The amine value of the urethane-based dispersing agent which functionsas a thixotropy suppressing agent is not particularly limited andpreferably 5 mgKOH/g to 70 mgKOH/g, and more preferably 8 mgKOH/g to 50mgKOH/g.

It is possible to use, for example, DISPERBYK-190, 191, 2013, 2009,2000, 2012, and 2001 (the above are all produced by BYK Japan K.K.),UVX-36 and 39 (the above are all produced by Kusumoto Chemicals, Ltd.),or the like as the acryl-based dispersing agent which functions as athixotropy suppressing agent.

The acid value of the acryl-based dispersing agent which functions as athixotropy suppressing agent is not particularly limited and ispreferably 0 mgKOH/g to 33 mgKOH/g, and more preferably 2 mgKOH/g to 30mgKOH/g.

The amine value of the acryl-based dispersing agent which functions as athixotropy suppressing agent is not particularly limited; however, 0mgKOH/g to 50 mgKOH/g is preferable, and 3 mgKOH/g to 30 mgKOH/g is morepreferable.

As the acrylic silicon-based dispersing agent which functions as athixotropy suppressing agent, it is possible to use, for example,UVX-270 and 272 (the above are all produced by Kusumoto Chemicals,Ltd.), or the like.

Regarding the fluorine-containing powder as a thixotropy suppressingagent, the region which includes at least a surface of the constituentparticles thereof is formed of a material which includes fluorine, andrefers to a component other than the metal powder.

By including the fluorine-containing powder as a thixotropy suppressingagent, in addition to the effects of improvement of the dischargestability by including a thixotropy suppressing agent, it is possible tomake the abrasion resistance or the like of the produced recorded matterparticularly excellent. In particular, when the constituent particles ofthe metal powder and the constituent particles of thefluorine-containing powder are both formed of a fluorine-based material,it is possible to favorably arrange the constituent particles of thefluorine-containing powder in the vicinity of the constituent particlesof the metal powder in the printed portion and to obtain a reliablyexcellent abrasion resistance at a higher level in the printed portion.

The fluorine-containing powder preferably has transparency in a curedproduct state where the polymerizable compound which forms theultraviolet-curable composition is cured. Due to this, it is possible tomake the aesthetic appearance of the recorded matter produced using theultraviolet-curable composition of the invention particularly excellent.

Here, in a cured product with a thickness of 100 μm which is formed bycuring an ultraviolet-curable composition which has the same compositionas the above apart from not including the metal powder, thetransmittance (the transmittance of light with a wavelength of 600 nm)of visible light in the thickness direction is preferably 85% or moreand more preferably 90% or more.

Due to this, since the fluorine-containing powder easily transmits lightfor curing a polymerizable compound, the curing of theultraviolet-curable composition easily uniformly advances to the innerside when forming the recorded matter and it is possible to make theaesthetic appearance of the recorded matter produced using theultraviolet-curable composition of the invention superior.

Regarding the constituent particles of the fluorine-containing powder,it is sufficient if the region which includes at least a surface isformed of a material which includes fluorine and it is possible to use,for example, particles which are formed of fluorine-based polymers,inorganic fine particles which are subjected to a treatment by afluorine-based surface treatment agent, or the like.

In particular, the fluorine-containing powder preferably includesparticles which are formed of fluorine-based polymers.

Due to this, it is possible to easily obtain fluorine-containing powderas a powder of which the particle diameter is small as will be describedbelow. In addition, it is possible to make the transparency particularlyexcellent in a cured product state where a polymerizable compound whichforms the ultraviolet-curable composition is cured. In addition, sincethe surface energy of the constituent particles is particularly smalland hydrophobic interaction with the polymerizable compound which isincluded in the ultraviolet-curable composition is particularly large,the constituent particles are easily stabilized by moving the gas-liquidinterface, the fluorine-containing powder is easily fixed on the surfaceof the recorded matter which is obtained by ultraviolet ray curing as aresult, and it is possible to make the abrasion resistance of therecorded matter particularly excellent.

In particular, in a case where the fluorine-containing powder includesparticles which are formed of fluorine-based polymers as constituentparticles, since the specific gravity is approximately 1.7 to 2.2, whichis lighter than metals such as aluminum, the flow in theultraviolet-curable composition occurs to the same extent as the metalpowder, thus the abrasion resistance of the recorded matter iseffectively improved with a smaller added amount.

In a case where the fluorine-containing powder includes particles whichare formed of fluorine-based polymers as the constituent particles,examples of the fluorine-based polymers include polytetrafluoroethylene,tetrafluoroethylene-hexafluoropropylene copolymers,tetrafluoroethylene-ethylene copolymers,tetrafluoroethylene-perfluoroalkyl vinyl ether copolymers,polychlorotrifluoroethylene, polyvinylidene fluoride, and the like, andpolytetrafluoroethylene is preferable among these. Due to this, thesurface energy of the fluorine-containing powder is particularly smalland it is possible to effectively improve the abrasion resistance of therecorded matter with a smaller added amount.

In addition, the constituent particles of the fluorine-containing powdermay be formed of dendritic polymers.

Due to this, it is possible to favorably obtain the fluorine-containingpowder as a powder of which the constituent particles are spheres andthe particle diameter is small as will be described below. In addition,it is possible to make the particle distribution of thefluorine-containing powder sharper.

In the invention, the dendritic polymer includes a dendrimer orhyperbranched polymer in a skeleton structure and is generally providedwith a core and dendrons in the case of dendrimer. On the other hand,the hyperbranched polymer has a single skeleton structure without thedistinction of a core or dendrons.

In a case where the constituent particles of the fluorine-containingpowder are formed of dendritic polymers (particularly dendrimers), asthe dendrimer (dendrimer which contains a fluorine atom), it is possibleto use, for example, dendritic polymers which are formed of polymerswhich have an acryl skeleton, polymers which have an epoxy skeleton,polymers which have a polyamide amine (PAMAM) skeleton, polymers whichhave a bis(hydroxymethyl) propanoic acid (MPA) skeleton, polymers whichhave a polypropylene imine skeleton, polymers which have a polylysineskeleton, polymers which have a polyphenyl ether skeleton, polymerswhich have a dithiocarbamate skeleton, and the like, and a dendriticpolymer formed of polymers which have an acryl skeleton or adithiocarbamate skeleton is particularly preferable.

Due to this, it is possible to make the transparency of the constituentparticles of the fluorine-containing powder in the printed portionparticularly excellent and to make the aesthetics (aesthetic appearance)of the recorded matter particularly excellent. In addition, since thedendritic polymer (dendrimer which contains a fluorine atom) which hasan acryl skeleton is excellent in compatibility with the polymerizablecompound which will be described below in detail, it is possible to makethe storage stability or the like of the ultraviolet-curable compositionparticularly excellent, it is possible to make the adhesiveness betweena polymer of a polymerizable compound and dendrimer which contains afluorine atom in the printed portion which is formed using theultraviolet-curable composition particularly excellent, and it ispossible to make the abrasion resistance, film strength, or the like ofthe printed portion particularly excellent.

Examples of the core of the dendrimer which contains a fluorine atominclude pentaerythritol hexaacrylate, trimethylolpropane triacrylate,pentaerythritol tetraacrylate, and the like which are bifunctional orhigher multifunctional acrylates.

Examples of the dendrons of the dendrimer (dendrimer which contains afluorine atom) which is included in the ultraviolet-curable compositionof the invention include trifunctional or higher multifunctionalacrylates and the like.

It is possible to use, for example, a dendrimer which is disclosed inJP-A-2002-220468, JP-A-2003-226611, JP-A-2009-235372, and the like asthe dendrimer which contains a fluorine atom and a fluorineatom-containing low molecule (a dendron constituent unit) which formsthe dendrimer.

In addition, as a dendritic polymer in a case where the dendriticpolymer (a dendritic polymer which contains a fluorine atom) which isincluded in the ultraviolet-curable composition is a hyperbranchedpolymer, it is possible to use, for example, the dendritic polymer whichhas a dithiocarbamate skeleton and which is disclosed in Japanese PatentApplication No. 2012-546933 (P2012-546933).

The surface free energy of the dendritic polymer which contains afluorine atom is preferably 18 mN/m to 28 mN/m, and more preferably 19mN/m to 25 mN/m.

Due to this, it is possible to make the abrasion resistance of theprinted portion particularly excellent while making the dischargestability of the ultraviolet-curable composition with an ink jet methodparticularly excellent.

In a case where the fluorine-containing powder includes inorganic fineparticles subjected to a treatment by a fluorine-based surface treatmentagent as constituent particles, examples of constituent material of theinorganic fine particles (base particles) include silica, alumina,titania, magnesium oxide, calcium oxide, mica, carbon black, glass,talc, aluminum hydroxide, magnesium hydroxide, asbestos, iron oxide,zinc oxide, calcium carbonate, barium sulfide, calcium sulfate,graphite, boron, and the like.

In particular, the inorganic fine particles (base particles) arepreferably formed of a material of which at least the surface has anoxide. Due to this, since it is possible for the fluorine-based surfacetreatment agent to react finely, the energy of the surface on which thefluorine-containing powder is the constituent particles is extremelysmall, a large number of fine particles are present on the surface ofthe recorded matter with a small added amount, and it is possible forthe fixed particles to form a convex shape at a sufficient height, thusit is possible to make the abrasion resistance particularly excellent.

In addition, the inorganic fine particles (base particles) arepreferably formed of one type or two or more types selected from amongthe material described above, particularly, a group formed of silica,alumina, and titania. Due to this, since it is possible to increase thehardness of the constituent particles of the fluorine-containing powder,a treatment with the fluorine-based surface treatment agent is easilyperformed, and the surface treatment with higher precision is possible,thus, even in a case where the content ratio of the fluorine-containingpowder in the ultraviolet-curable composition is made to be lower, it ispossible to make the abrasion resistance and durability of the recordedmatter produced using the ultraviolet-curable composition sufficientlyexcellent. In addition, since it is possible to make the transparency ofthe fluorine-containing powder particularly high, it is possible to morereliably make the aesthetic appearance of the recorded matter producedusing the ultraviolet-curable composition excellent.

In particular, in a case where the base particles (the inorganic fineparticles) are formed of silica, the following effects are obtained.That is, silica is a material with high reactivity with a fluorine-basedsilane compound as the fluorine-based surface treatment agent and is amaterial with particularly high transparency and high hardness (Mohshardness 7). For this reason, it is possible to make the abrasionresistance and durability of the recorded matter produced using theultraviolet-curable composition superior. In addition, it is possible tomore reliably make the aesthetic appearance of the recorded matter whichis produced using the ultraviolet-curable composition excellent. Inaddition, since silica is a material at a low cost with highversatility, it is also preferable from the point of view of reductionin the production cost of the ultraviolet-curable composition and therecorded matter and stable supply of the ultraviolet-curable compositionand the recorded matter.

In addition, in a case where the base particles are formed of alumina,the following effects are obtained. That is, alumina is a material withhigh reactivity with a fluorine-based silane compound as thefluorine-based surface treatment agent and a material with particularlyhigh transparency and high hardness (Mohs hardness 9). For this reason,it is possible to make the abrasion resistance and durability of therecorded matter produced using the ultraviolet-curable compositionsuperior. In addition, it is possible to more reliably make theaesthetic appearance of the recorded matter which is produced using theultraviolet-curable composition excellent. In addition, since alumina isa material with high versatility at a low cost, it is also preferablefrom the point of view of reducing the production cost of theultraviolet-curable composition and the recorded matter and stablesupply of the ultraviolet-curable composition and the recorded matter.

In addition, in a case where the base particles are formed of titania,the following effects are obtained. That is, titania is a material withparticularly high transparency and high hardness (Mohs hardness 7 to7.5). For this reason, it is possible to make the abrasion resistanceand durability of the recorded matter produced using theultraviolet-curable composition superior. In addition, it is possible tomore reliably make the aesthetic appearance of the recorded matter whichis produced using the ultraviolet-curable composition excellent. Inaddition, since titania is a material with high versatility at a lowcost, it is also preferable from the point of view of reducing theproduction cost of the ultraviolet-curable composition and the recordedmatter and stable supply of the ultraviolet-curable composition and therecorded matter. In addition, titania has extremely high stability andhigh resistance to reactive gases such as hydrogen fluoride, hydrogensulfide, SO₃, and chlorine.

In a case where the fluorine-containing powder includes inorganic fineparticles subjected to a treatment by a fluorine-based surface treatmentagent as constituent particles, it is possible to use an agent whichincludes at least one fluorine atom in the molecule as thefluorine-based surface treatment agent and it is possible to use, forexample, the fluorine-based compound (the fluorine-based surfacetreatment agent) which is described as a surface treatment agent withrespect to the metal powder (base particles) described above. In moredetail, examples thereof include compounds (a fluorine-based short chaincompound, a fluorine-based long chain compound, a fluorine-based silanecompound, a fluorine-based phosphate compound, a fluorine-substitutedfatty acid, a fluorine-based isocyanate compound, and the like) whichhave a structure in which at least some of the hydrogen atoms of theshort chain compound, the long chain compound, the silane compound, thephosphate compound, the carboxylic acid, and the isocyanate compounddescribed above are substituted by fluorine atoms or the like.

In particular, in a case of using the fluorine-based silane compound,since the reactivity with silica and alumina is high, it is possible tomore stably disperse the constituent particles of thefluorine-containing powder formed of inorganic fine particles which areformed of the inorganic material subjected to a treatment by afluorine-based silane compound as the fluorine-based surface treatmentagent in the ultraviolet-curable composition.

In addition, in a case of using the fluorine-based phosphate compound,it is possible to more effectively perform the surface treatment withthe inorganic fine particles which are formed of iron oxide, aluminum,alumina, and the like. In addition, since the surface treatment agent ofthe phosphate compound is strong against acid, the obtained recordedmatter exhibits excellent durability and weather resistance even underan acidic environment.

In addition, in a case of using a fluorine-substituted fatty acid (afluorine-based fatty acid), since the reactivity with calcium carbonateand titania is high, it is possible to more stably disperse theconstituent particles of the fluorine-containing powder formed ofinorganic fine particles which are formed of the inorganic materialsubjected to a treatment by a fluorine-substituted fatty acid as thefluorine-based surface treatment agent in the ultraviolet-curablecomposition.

In addition, in a case of using a fluorine-based isocyanate compound, itis possible to make the bonding force of the base particles (inorganicfine particles) and the surface treatment agent particularly strong.

In a case where the fluorine-containing powder includes inorganic fineparticles subjected to a treatment by a fluorine-based surface treatmentagent as constituent particles, the fluorine-based surface treatmentagent which is used for the surface treatment of inorganic fineparticles and the fluorine-based surface treatment agent which is usedfor the surface treatment of the constituent particles of the metalpowder may be the same type of surface treatment agent. Due to this, bythe surface characteristics (interface energy, a charged state, and thelike) of both the metal powder and the fluorine-containing powder beingsimilar, the stability of dispersion in the ultraviolet-curablecomposition is particularly excellent and it is possible to moreeffectively suppress increases in the viscosity or particle size over alonger period.

The average particle diameter (D₅₀) of the fluorine-containing powder ispreferably 1 nm to 50 nm, more preferably 2 nm to 10 nm, and even morepreferably 2.5 nm to 9 nm.

Due to this, it is possible to make the discharge stability of theultraviolet-curable composition particularly excellent. In addition, itis possible to make the storage stability of the ultraviolet-curablecomposition particularly excellent and to make the glossiness andabrasion resistance of the printed portion which is formed using theultraviolet-curable composition particularly excellent.

When the thickness of the metal powder is T_(M) [μm] and the averageparticle diameter of the fluorine-containing powder is D_(F) [μm], arelationship of 0.05≤D_(F)/T_(M)≤0.7 is preferably satisfied, arelationship of 0.07≤D_(F)/T_(M)≤0.5 is more preferably satisfied, and arelationship of 0.10≤D_(F)/T_(M)≤0.35 is even more preferably satisfied.

Due to this, it is possible to more effectively prevent the constituentparticles of the fluorine-containing powder from being excessivelypresent on the outer surface side (the viewing side of an observer)compared to the constituent particles of the metal powder in therecorded matter, it is possible to make the glossiness of the printedportion superior, and it is possible to make the abrasion resistance ofthe recorded matter particularly excellent.

When the average particle diameter of the metal powder is D_(M) [μm] andthe average particle diameter of the fluorine-containing powder is D_(F)[μm], a relationship of 5≤D_(M)/D_(F)≤300 is preferably satisfied, arelationship of 15≤D_(M)/D_(F)≤200 is more preferably satisfied, and arelationship of 25≤D_(M)/D_(F)≤200 is even more preferably satisfied.

Due to this, it is possible to make the glossiness of the printedportion superior and it is possible to make the abrasion resistance ofthe recorded matter particularly excellent.

The particles which form the fluorine-containing powder may take anyshape such as a sphere, a spindle, a needle (a bar shape), or flakes,but preferably form spheres.

Due to this, it is possible to make the abrasion resistance of therecorded matter produced using the ultraviolet-curable compositionparticularly excellent. In addition, in a case where the particles whichform the fluorine-containing powder form spheres, it is possible to moreeffectively prevent the fluorine-containing powder from having anadverse influence on the appearance of the recorded matter, while makingthe content ratio of the fluorine-containing powder in theultraviolet-curable composition (in the printed portion) high and moreeffectively exhibiting the effects of including the fluorine-containingpowder described above.

In addition, in a case where the particles which form thefluorine-containing powder are spindle-shaped or bar-shaped, since thespecific surface area of the particles which forms thefluorine-containing powder is large, the particles easily come to thesurface in the ultraviolet-curable composition which is added onto therecording medium, it is possible to more favorably arrange the particlesin the vicinity of the outer surface of the printed portion, and it ispossible to make the abrasion resistance excellent even with acomparatively small content ratio.

In addition, in a case where the particles which form thefluorine-containing powder are spindle-shaped, since the area isincreased by balancing and orienting a long axis direction of thespindle shape with the surface so as to come into contact therewith orthe particles are hardened and fixed in a state of being deep in therecorded matter, an effect of further reinforcing the abrasionresistance of the recorded matter is also obtained.

The content ratio of the thixotropy suppressing agent in theultraviolet-curable composition is preferably 0.2 mass % to 2.0 mass %,more preferably 0.3 mass % to 1.5 mass %, and even more preferably 0.5mass % to 1.0 mass %.

Due to this, it is possible to make the discharge stability of anultraviolet-curable composition with an ink jet method particularlyexcellent and make the productivity of the recorded matter and thereliability of the recorded matter particularly excellent, and it isalso possible to make the glossiness, the abrasion resistance, and thelike of the recorded matter particularly excellent.

Substance A

In addition, the ultraviolet-curable composition of the inventionpreferably includes a substance A which has a partial structure which isshown by Formula (8).

(In Formula (8), R¹ indicates an oxygen atom, a hydrogen atom, ahydrocarbon group, or an alkoxyl group and R², R³, R⁴, and R⁵ eachindependently indicate a hydrogen atom or a hydrocarbon group.)

By the ultraviolet-curable composition including the substance A whichhas the chemical structure along with the thixotropy suppressing agentdescribed above and moreover including a monomer which has an alicyclicstructure, it is possible to make the storage stability, curability, anddischarge stability of the ultraviolet-curable composition with an inkjet method particularly excellent. In addition, in the recorded matterproduced using the ultraviolet-curable composition, it is possible tomore effectively exhibit the natural glossiness and sense of luxury ofthe metal material which forms the metal powder, make the glossiness andabrasion resistance of the printed portion particularly excellent, andmake the durability of the recorded matter particularly excellent.

In Formula (8), it is sufficient if R¹ is an oxygen atom, a hydrogenatom, a hydrocarbon group, or an alkoxyl group (a group in which a chainor alicyclic hydrocarbon group is bonded with an oxygen atom); however,a hydrogen atom, a methyl group, or an octyloxy group is particularlypreferable.

Due to this, it is possible to make the storage stability and dischargestability of the ultraviolet-curable composition superior and it ispossible to make the glossiness and abrasion resistance of the printedportion which is formed using the ultraviolet-curable compositionsuperior.

In addition, in Formula (8), it is sufficient if R² to R⁵ are eachindependently a hydrogen atom or a hydrocarbon group; however, an alkylgroup with 1 to 3 carbon atoms is preferable, and a methyl group is morepreferable.

Due to this, it is possible to make the storage stability and dischargestability of the ultraviolet-curable composition superior and it ispossible to make the glossiness and abrasion resistance of the printedportion which is formed using the ultraviolet-curable compositionsuperior.

The content ratio of the substance A in the ultraviolet-curablecomposition is preferably 0.1 mass % to 5.0 mass % and more preferably0.5 mass % to 3.0 mass %.

Due to this, it is possible to make the storage stability, dischargestability, and curability of the ultraviolet-curable compositionsuperior and it is also possible to make the glossiness, abrasionresistance, and the like of the recorded matter produced using theultraviolet-curable composition superior. Here, the ultraviolet-curablecomposition may include two or more types of compounds as the substanceA. In this case, the total of the content ratio of the compounds ispreferably a value within these ranges.

When the content ratio of the substance A is X_(A) [mass %] and thecontent ratio of the metal powder is X_(M) [mass %], a relationship of0.01≤X_(A)/X_(M)≤0.8 is preferably satisfied and a relationship of0.05≤X_(A)/X_(M)≤0.4 is more preferably satisfied.

By satisfying the relationship, it is possible to make the storagestability and discharge stability of the ultraviolet-curable compositionsuperior and it is possible to make the glossiness and abrasionresistance of the printed portion which is formed using theultraviolet-curable composition superior.

Defoaming Agent

The ultraviolet-curable composition may include a defoaming agent as anadditive.

Since it is possible for the defoaming agent to reduce the surfacetension of the ultraviolet-curable composition and greatly reduce airbubbles which are generated at the meniscus position in the vicinity ofthe nozzles, it is possible to make the discharge stability in the inkjet of the ultraviolet-curable composition excellent.

In contrast, in a case where the ultraviolet-curable composition doesnot contain a defoaming agent, by the pigment or fluorine-containingparticles subjected to a treatment by a fluorine-based surface treatmentagent with low surface free energy being easily arrayed on a gas-liquidinterface in the air bubbles which are generated in theultraviolet-curable composition, it is possible for the air bubbles tobe stably present for a long time. As the result, discharge energy whichis generated from piezoelectric elements or the like in an ink jetmethod being absorbed or attenuated in the stabilized air bubbles causesvarious problems such as discharge failures, decreases in the liquiddroplet weight, decrease in the flying speed of liquid droplets, orbending in the flying direction. For this reason, it is not possible tosufficiently make the discharge stability excellent and the uniformityof the ultraviolet-curable composition also remarkably deteriorates.

In particular, it is possible to make the discharge stability excellentby using an acryl-based defoaming agent which includes fluorine or anacryl-based defoaming agent which does not have a polar functional groupas a defoaming agent. Since the molecular weight of the defoaming agentsis small and the dispersing and moving speed is extremely fast comparedto the pigment or fluorine-containing particles subjected to a treatmentby a fluorine-based surface treatment agent, it is possible toeffectively suppress the generation of air bubbles.

Specific examples of the acryl-based defoaming agent which includesfluorine which is able to be used in the invention include BYK-3440(produced by BYK Japan K.K.), BYK-3441 (produced by BYK Japan K.K.), andthe like.

In addition, the acryl-based defoaming agent which does not have a polarfunctional group which is able to be used in the invention is an acrylcopolymer which does not have a functional group such as a hydroxylgroup, an amino group, a carboxyl group, a cyano group, and a ketonegroup of which the electronegativity is high in a molecule as a polarfunctional group, and specific examples thereof include DISPERBYK-354(produced by BYK Japan K.K.), DISPERBYK-392 (produced by BYK JapanK.K.), and the like.

The content of the defoaming agent is preferably 1.5 weight % or lessand more preferably 0.1 weight % to 1.0 weight %.

Due to this, it is possible to make the storage stability, dischargestability, and curability of the ultraviolet-curable compositionsuperior, while making the glossiness of the recorded matter producedusing the ultraviolet-curable composition sufficiently excellent. Here,the defoaming agent may include two or more types of compounds as theacryl-based defoaming agent which includes fluorine or the acryl-baseddefoaming agent which does not have a polar functional group.

In this case, the total of the content ratio of the compounds ispreferably a value within these ranges. Here, when the content ratio ofthe defoaming agent in the ultraviolet-curable composition is extremelyhigh, it is difficult to favorably arrange the metal powder andfluorine-containing powder in the vicinity of the outer surface of theultraviolet-curable composition due to the concentration of the excessdefoaming agent which does not affect defoaming being increased andthere is a possibility that it will be difficult to make the glossinessand abrasion resistance of the recorded matter (printed portion) whichis finally obtained sufficiently excellent.

Other Components

The ultraviolet-curable composition of the invention may includecomponents (other components) other than the components described above.Examples of the components include photopolymerization initiators,slipping agents (a levelling agent), solvents, polymerization promotors,polymerization inhibitors, dispersing agents which do not function as athixotropy suppressing agent, permeation promotors, moistening agents (amoisturizer), coloring agents, fixing agents, antifungal agents,preservative agents, antioxidants, chelating agents, viscositythickening agents, radiosensitizing agents (radiosensitizing pigments),and the like.

The photopolymerization initiator is not particularly limited as long asthe photopolymerization initiator generates an active species such asradicals or cations by being irradiated with ultraviolet rays andinitiates the polymerization reaction of the polymerizable compounddescribed above. As the photopolymerization initiator, it is possible touse a photo-radical polymerization initiator or a photo-cationpolymerization initiator; however, a photo-radical polymerizationinitiator is preferably used. In a case of using a photopolymerizationinitiator, the photopolymerization initiator preferably has anabsorption peak in an ultraviolet ray region.

Examples of the photo-radical polymerization initiator include aromaticketones, acyl phosphine oxide compounds, aromatic onium salt compounds,organic peroxide, thio compound (thioxanthone compounds, thiophenylgroup-containing compounds, and the like), hexaarylbiimidazolecompounds, ketoxime ester compounds, borate compounds, aziniumcompounds, metallocene compounds, active ester compounds, compoundswhich have a carbon halogen bond, alkylamine compounds, and the like.

Among these, from the point of view of the solubility in a polymerizablecompound and curability, at least one type selected from an acylphosphine oxide compound and a thioxanthone compound is preferable, andthe use of an acyl phosphine oxide compound and a thioxanthone compoundtogether is more preferable.

Specific examples of the photo-radical polymerization initiator includeacetophenone, acetophenone benzyl ketal, 1-hydroxy cyclohexyl phenylketone, 2,2-dimethoxy-2-phenylacetophenone, xanthone, fluorenone,benzaldehyde, fluorene, anthraquinone, triphenylamine, carbazole,3-methylacetophenone, 4-chloro benzophenone, 4,4′-dimethoxybenzophenone, 4,4′-diaminobenzophenone, Michler's ketone, benzoin propylether, benzoin ethyl ether, benzyl dimethyl ketal, 1-(4-isopropylphenyl)-2-hydroxy-2-methyl propan-1-one, 2-hydroxy-2-methyl-1-phenylpropan-1-one, thioxanthone, diethylthioxanthone,2-isopropylthioxanthone, 2-chlorothioxanthone,2-methyl-1-[4-(methylthio) phenyl]-2-morpholino-propan-1-one,bis(2,4,6-trimethyl benzoyl)-phenyl phosphine oxide, 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide, 2,4-diethylthioxanthone,bis-(2,6-dimethoxybenzoyl)-2,4,4-trimethyl pentyl phosphine oxide andthe like, and one type or two or more types selected from among thesecan be used in combination.

The content of the photopolymerization initiator in theultraviolet-curable composition is preferably 0.5 mass % to 10 mass %.

When the content of the photopolymerization initiator is in this range,the ultraviolet ray curing speed is sufficiently high and there islittle undissolved remaining photopolymerization initiator or coloringwhich is derived from the photopolymerization initiator.

When the ultraviolet-curable composition includes a slipping agent, thesurface of the recorded matter is smooth due to the levelling effect andthe abrasion resistance is improved.

It is possible to use a slipping agent without being particularlylimited, and examples thereof include silicone-based surfactants such aspolyester-modified silicone, polyether-modified silicone, andpolyacrylate-modified silicone, and polymer-based surfactants such aspolyacrylate, and polyester, and polyether-modifiedpolydimethylsiloxane, polyester-modified polydimethylsiloxane, orpolyacrylate-modified dimethylsiloxane are preferably used.

Here, the ultraviolet-curable composition of the invention may include apolymerization inhibitor; however, even in a case of including apolymerization inhibitor, the content ratio of the polymerizationinhibitor in the ultraviolet-curable composition is preferably 0.6 mass% or less and more preferably 0.3 mass % or less.

Due to this, since it is possible to make the content ratio of thepolymerizable compound in the ultraviolet-curable composition relativelyhigh, it is possible to make the abrasion resistance or the like of theprinted portion which is formed using the ultraviolet-curablecomposition particularly excellent.

In addition, the ultraviolet-curable composition of the inventionpreferably does not include an organic solvent which is removed(evaporated) in a step of producing the recorded matter. Due to this, itis possible to effectively prevent the occurrence of the problem ofvolatile organic compounds (VOC).

Recorded Matter

Next, description will be given of the recorded matter of the invention.

The recorded matter of the invention is produced by adding theultraviolet-curable composition described above onto a recording mediumwith an ink jet method and then irradiating the ultraviolet-curablecomposition with the ultraviolet rays. That is, the recorded matter ofthe invention is provided with a cured product of theultraviolet-curable composition described above and a recording medium.

The recorded matter has a pattern (a printed portion) with excellentglossiness and in which the generation of defects is prevented.

As described above, the ultraviolet-curable composition according to theinvention includes a polymerizable compound and is excellent in adhesionwith respect to a recording medium. In this manner, since theultraviolet-curable composition of the invention is excellent inadhesion to a recording medium, the recording medium may be any mediumand either absorbent or non-absorbent media may be used, and it ispossible to use, for example, paper (plain paper, ink jet specialtypaper, and the like), plastic material, metal, ceramics, woodenmaterial, shells, cotton, polyester, natural fiber and synthetic fibersuch as wool, non-woven fabric, and the like. In addition, the shape ofthe recording medium is not particularly limited and may be any shape,such as a sheet.

As the liquid droplet discharging method (the ink jet method), it ispossible to use a piezo method, a method of discharging ink by foam(bubbles) which are generated by heating the ink, or the like; however,from the point of view of difficulty in degeneration of theultraviolet-curable composition or the like, a piezo method ispreferable.

It is possible to discharge the ultraviolet-curable composition with anink jet method using a liquid droplet discharging apparatus which isknown in the art.

The frequency relating to the discharge of the ultraviolet-curablecomposition with an ink jet method is preferably 8 kHz or more and morepreferably 12 kHz to 60 kHz.

Due to this, it is possible to make the productivity of the recordedmatter particularly excellent. In addition, while the problem ofdischarge failure of the ultraviolet-curable composition occursparticularly easily in the background art, when performing the dischargewith an ink jet method in the high frequency region, it is possible toeffectively prevent the occurrence of the problem described above in theinvention even in a case of discharging in the high frequency region.That is, when the frequency relating to the discharge of theultraviolet-curable composition with an ink jet method is a value in therange described above, the effects according to the invention are moreremarkably exhibited.

The ultraviolet-curable composition which is discharged with an ink jetmethod is cured by being irradiated with ultraviolet rays.

As an ultraviolet ray source, it is possible to use, for example, amercury lamp, a metal halide lamp, an ultraviolet light emitting diode(UV-LED), an ultraviolet laser diode (UV-LD), and the like. Among these,an ultraviolet light emitting diode (UV-LED) and an ultraviolet laserdiode (UV-LD) are preferable from the point of view of miniaturization,long life, high efficiency, and low costs.

The recorded matter of the invention may be for any use and, forexample, may be applied to a decorative material or other use. Specificexamples of the recorded matter of the invention include vehicularinterior components such as a console lid, a switch base, a centercluster, an interior panel, an emblem, a center console, and a metername plate, operation portions (key switches) of various types ofelectronic equipment, a decorative portion which exhibits a decorativeproperty, an index, objects for display such as logos, and the like.

Description was given above of aspects of the invention based onfavorable embodiments; however, the invention is not limited thereto.

For example, in the embodiment described above, description was mainlygiven of the case where the recorded matter of the invention is formedby a recording medium (a substrate) and a printed portion; however, therecorded matter of the invention may have other configurations inaddition to the recording medium (substrate) and the printed portion.

EXAMPLE

Next, description will be given of specific examples of the invention.

1. Producing Ultraviolet-Curable Composition (Ultraviolet-Curable InkJet Composition) Example 1

Firstly, a film (with a surface roughness Ra of 0.02 μm or less) made ofpolyethylene terephthalate with a smooth surface is prepared.

Next, silicone oil is coated on the entirety of one surface of the film.

Next, a film which is formed of Al is formed on the surface side onwhich silicone oil is coated by a vapor deposition method.

Next, a film (a substrate) made of polyethylene terephthalate on which afilm of Al was formed was inserted in a liquid which was formed bydissolving CF₃(CF₂)₅(CH₂)₂O—PO(OH)₂: 1 part by mass as a fluorine-basedsurface treatment agent in diethylene glycol diethyl ether: 99 parts bymass, and ultrasonic vibration of 27 kHz was applied thereto at 55° C.for 3 hours. Due to this, a dispersing liquid of the metal powder formedof flaky particles where base particles made of Al were subjected to asurface treatment using CF₃(CF₂)₅(CH₂)₂O—PO(OH)₂ is obtained.

The volume average particle diameter of the metal powder which wasobtained in this manner was 0.45 μm, the particle diameter (D₁₀) at thevolume accumulation distribution ratio 10% from the fine particle sideof the metal powder was 0.28 μm, the particle diameter (D₉₀) at thevolume accumulation distribution ratio 90% from the fine particle sideof the metal powder was 0.77 μm, and the half-value width in theparticle distribution of the metal powder was 0.32 μm.

Next, the ultraviolet-curable composition is obtained by mixing thedispersing liquid of the metal powder with acryloylmorpholine as amonomer (a polymerizable compound) which has an alicyclic structure,phenoxyethyl acrylate as a monomer (a polymerizable compound) which doesnot have an alicyclic structure, tetrahydrofurfuryl acrylate as amonomer (a polymerizable compound) which has an alicyclic structure,Disperbyk-118 (a phosphoric acid-based dispersing agent) as a thixotropysuppressing agent, the substance A which has a chemical structure whichis represented by Formula (9) described below, Irgacure 819 (produced byBASF Corp.) as a photopolyerization initiator, Speedcure TPO (producedby ACETO Corp.) as a photopolyerization initiator, Speedcure DETX(produced by Lambson Ltd.) as a photopolyerization initiator, andLF-1982 (produced by Kusumoto Chemicals, Ltd.).

Examples 2 to 20

The ultraviolet-curable compositions were produced in the same manner asExample 1 apart from forming the constituent particles of the metalpowder as shown in Table 1 and making the compositions as shown in Table2 and Table 3 by changing the types and ratios of the raw materials usedfor preparation of the ultraviolet-curable composition.

Comparative Example 1

The ultraviolet-curable composition was produced in the same manner asExample 1 apart from not using a thixotropy suppressing agent and makingthe compositions as shown in Table 3 by changing the types and ratios ofthe raw material used for preparation of the ultraviolet-curablecomposition.

Comparative Example 2

The ultraviolet-curable composition was produced in the same manner asExample 1 apart from making the composition as shown in Table 3 bychanging the types and ratios of the raw materials used for preparationof the ultraviolet-curable composition.

Regarding each of the Examples and Comparative Examples, theconfigurations of the metal powder which is included in theultraviolet-curable composition are shown together in Table 1 and thecompositions of the ultraviolet-curable composition are shown togetherin Table 2 and Table 3. Here, in the tables, CF₃(CF₂)₅(CH₂)₂O—PO(OH)₂ asa fluorine-based phosphate compound is shown as “FAP1”,(CF₃(CF₂)₇CH₂CH₂Si(OC₂H₅)₃) as a fluorine-based silane compound as“FAS1”, (CF₃(CF₂)₅CH₂CH₂Si(OC₂H₅)₃) as a fluorine-based silane compoundas “FAS2”, CF₃(CF₂)₇(CH₂)₂COOH as a fluorine-substituted fatty acid as“FFA1”, CF₃(CF₂)₇(CH₂)₂NCO as a fluorine-based isocyanate compound as“IS1”, lauryl phosphoric acid: CH₃(CH₂)₁₁—(OCH₂CH₂)₂—O—PO(OH)₂ as analkylphosphate compound as “LAP”, laures-2 phosphoric acid:CH₃(CH₂)₁₁—(OCH₂CH₂)₂—O—PO(OH)₂ as an alkyl ether phosphate compound as“LEP”, octyl triethoxy silane as an alkyl silane compound as “OTS”,CH₃(CH₂)₇O—PO(OH)₂ as “AP1”, γ-butyrolactone acrylate as a monomer (apolymerizable compound) which has an alicyclic structure as “BLA”,tetrahydrofurfuryl acrylate as a monomer (a polymerizable compound)which has an alicyclic structure as “THFA”, N-vinylcaprolactam as amonomer (a polymerizable compound) which has an alicyclic structure as“VC”, N-vinylpyrrolidone as a monomer (a polymerizable compound) whichhas an alicyclic structure as “VP”, acryloylmorpholine as a monomer (apolymerizable compound) which has an alicyclic structure as “AMO”,tris(2-acryloyloxyethyl)isocyanurate as a monomer (a polymerizablecompound) which has an alicyclic structure as “TAOEI”,dicyclopentenyloxyethyl acrylate as a monomer (a polymerizable compound)which has an alicyclic structure as “DCPTeOEA”, adamantyl acrylate as amonomer (a polymerizable compound) which has an alicyclic structure asdimethylol tricyclodecane diacrylate as a monomer (a polymerizablecompound) which has an alicyclic structure as “DMTCDDA”, dimethyloldicyclopentane diacrylate as a monomer (a polymerizable compound) whichhas an alicyclic structure as “DMDCPTA”, dicyclopentenyl acrylate as amonomer (a polymerizable compound) which has an alicyclic structure as“DCPTeA”, dicyclopentanyl acrylate as a monomer (a polymerizablecompound) which has an alicyclic structure as “DCPTaA”, isobornylacrylate as a monomer (a polymerizable compound) which has an alicyclicstructure as “IBA”, cyclohexyl acrylate as a monomer (a polymerizablecompound) which has an alicyclic structure as “CHA”, diacrylatedisocyanurate as a monomer (a polymerizable compound) which has analicyclic structure as “DAI”, triacrylated isocyanurate as a monomer (apolymerizable compound) which has an alicyclic structure as “TAI”,γ-butyrolactone methacrylate as a monomer (a polymerizable compound)which has an alicyclic structure as “BLM”, tetrahydrofurfurylmethacrylate as a monomer (a polymerizable compound) which has analicyclic structure as “THFM”, dicyclopentenyloxyethyl methacrylate as amonomer (a polymerizable compound) which has an alicyclic structure as“DCPTeOEM”, adamantyl methacrylate as a monomer (a polymerizablecompound) which has an alicyclic structure as “AM”, pentamethylpiperidylmethacrylate as a monomer (a polymerizable compound) which has analicyclic structure as “PMPM”, tetramethylpiperidyl methacrylate as amonomer (a polymerizable compound) which has an alicyclic structure as“TMPM”, 2-methyl-2-adamantyl methacrylate as a monomer (a polymerizablecompound) which has an alicyclic structure as “MAM”, 2-ethyl-2-adamantylmethacrylate as a monomer (a polymerizable compound) which has analicyclic structure as “EAM”, mevalonic lactone methacrylate as amonomer (a polymerizable compound) which has an alicyclic structure as“MLM”, dicyclopentenyl methacrylate as a monomer (a polymerizablecompound) which has an alicyclic structure as “DCPTeM”, dicyclopentanylmethacrylate as a monomer (a polymerizable compound) which has analicyclic structure as “DCPTaM”, isobornyl methacrylate as a monomer (apolymerizable compound) which has an alicyclic structure as “IBM”,cyclohexyl methacrylate as a monomer (a polymerizable compound) whichhas an alicyclic structure as “CHM”,cyclohexanespiro-2-(1,3-dioxolane-4-il) methyl acrylate as a monomer (apolymerizable compound) which has an alicyclic structure as “CHDOLA”,(2-methyl-2-ethyl-1,3-dioxolane-4-il) methyl acrylate as a monomer (apolymerizable compound) which has an alicyclic structure as “MEDOLA”,phenoxyethyl acrylate as a monomer (a polymerizable compound) which doesnot have an alicyclic structure as “PEA”, dipropylene glycol diacrylateas a monomer (a polymerizable compound) which does not have an alicyclicstructure as “DPGDA”, tripropylene glycol diacrylate as a monomer (apolymerizable compound) which does not have an alicyclic structure as“TPGDA”, 2-hydroxy-3-phenoxypropyl acrylate as a monomer (apolymerizable compound) which does not have an alicyclic structure as“HPPA”, 4-hydroxybutyl acrylate as a monomer (a polymerizable compound)which does not have an alicyclic structure as “HBA”, ethyl carbitolacrylate as a monomer (a polymerizable compound) which does not have analicyclic structure as “ECA”, methoxy triethylene glycol acrylate as amonomer (a polymerizable compound) which does not have an alicyclicstructure as “MTEGA”, t-butyl acrylate as a monomer (a polymerizablecompound) which does not have an alicyclic structure as “TBA”, benzylacrylate as a monomer (a polymerizable compound) which does not have analicyclic structure as “BA”, acrylic acid 2-(2-hydroxyethoxy) ethyl as amonomer (a polymerizable compound) which does not have an alicyclicstructure as “VEEA”, benzyl methacrylate as a monomer (a polymerizablecompound) which does not have an alicyclic structure as “BM”, urethaneacrylate as a monomer (a polymerizable compound) which does not have analicyclic structure as “UA”, DISPERBYK-118 as a thixotropy suppressingagent (a phosphoric acid-based dispersing agent) as “T1”, DISPERBYK-140as a thixotropy suppressing agent (an amine-based dispersing agent) as“T2”, polytetrafluoroethylene powder (volume average particle diameter(D₅₀): 51 nm, D₁₀: 11 nm, D₉₀: 89 nm, half-value width in particledistribution: 33 nm) as a thixotropy suppressing agent(fluorine-containing powder) as “T3”, FA-200F (volume average particlediameter: 7.5 nm, surface free energy: 19 mN/m) as a dendritic polymer(a hyperbranched polymer) which contains a fluorine atom as a thixotropysuppressing agent (fluorine-containing powder) as “T4”, DISPERBYK-110 asa thixotropy suppressing agent (a phosphoric acid-based dispersingagent) as “T5”, DISPERBYK-102 as a thixotropy suppressing agent (aphosphoric acid-based dispersing agent) as “T6”, Prisurf A212C as athixotropy suppressing agent (a phosphoric acid-based dispersing agent)as “T7”, the compound (the substance A) which is represented by Formula(9) described above as “A1”, the compound (the substance A) which isrepresented by Formula (10) described below as “A2”, the compound (thesubstance A) which is represented by Formula (11) described below as“A3”, the substance A which is represented by Formula (12) describedbelow as “A4”, Irgacure 819 (produced by BASF Corp.) as “ic819”,Speedcure TPO (produced by ACETO Corp.) as “scTPO”, Speedcure DETX(produced by Lambson Ltd.) as “scDETX”, BYK-350 (produced by BYK JapanK.K.) as “BYK 350”, hydroquinone monomethyl ether as “MEHQ”, LHP-96(produced by Kusumoto Chemicals, Ltd.) as “LHP”, LF-1982 (produced byKusumoto Chemicals, Ltd.) as “LF-1”, and LF-1984 (produced by KusumotoChemicals, Ltd.) as “LF-2”. In addition, in the tables, regardingExample 15, regarding the composition of the constituent material of thebase particles, the content ratio of each element is shown by weightratio. In addition, Table 2 and Table 3 show the value of η2−η1 for theultraviolet-curable compositions of each Example and Comparative Examplewhen a viscosity η1 [mPa·s] at a shearing speed 1000 sec⁻¹ and aviscosity η2 [mPa·s] which is obtained by measuring in a state where theshearing speed is set as 10 sec⁻¹ after continuously adding shearingstress at a shearing speed 1000 sec⁻¹ for 10 minutes are set, theviscosity η0 in a state (in a default state which is previously measuredby a vibration method or the like) before adding the shearing stress ata shearing speed of 1000 sec⁻¹, the value of η1−η0, and the value ofη1/η0. In addition, the measurement of the viscosity described above isperformed using a vibration-type viscometer (manufactured by A&DCompany, Ltd., SV-10A) for the viscosity η0 in a default state and themeasurement of the viscosities η1 and η2 which come along with shearingstress is performed using a rotational viscometer (manufactured by AntonPaar Japan K.K., Physica MCR-301). The environmental temperature whenmeasuring the shearing speed is 20° C. in all cases. In addition, 10arbitrary metal particles of each the metal powders forming theultraviolet-curable composition in each of the Examples were observed,the ratio (S₁/S₀) was determined with respect to an area S₁ [μm²] whenobserved (when viewing in plan view) from the direction in which theprojection area is the maximum and an area S₀ [μm²] when observed from adirection in which the area is the maximum when observing in thedirection orthogonal to the observation direction, and the average valuethereof was obtained, at which point the average values of S₁/S₀ wereall 19 or more.

(Here, the substance A shown in Formula (12) is a mixture of a pluralityof compounds in which n in the formula is 10 or more to 19 or less (themain component is a compound in which n in the formula is 15 or more to18 or less).)

TABLE 1 Metal powder Fluorine-containing powder Volume VolumeConstituent Material average Half- Constituent Material average materialused in particle value Average material used in particle of base surfacediameter D₁₀ D₉₀ width thickness of base surface diameter Shapeparticles treatment [μm] [μm] [μm] [μm] [nm] Shape particles treatment[nm] Example 1 Flaky Al FAP1 0.45 0.28 0.77 0.32 20 Sphere FA-1 — 7Example 2 Flaky Al FAP1 0.45 0.28 0.77 0.32 20 Sphere FE-1 — 10 Example3 Flaky Al FAP1 0.76 0.45 1.36 0.84 20 Sphere FMP-1 — 22 Example 4 FlakyAl FAP1 0.95 0.51 1.75 1.12 80 Sphere Silica FAS1 36 Example 5 Flaky AlFAP1 0.95 0.51 1.75 1.12 80 Sphere Alumina FAS1 30 Example 6 Flaky AlFAP1 0.79 0.44 1.36 0.86 60 Sphere Silica FAS2 36 Example 7 Flaky AlFAP1 0.79 0.44 1.36 0.86 60 Sphere Alumina FAS2 30 Example 8 Flaky AlFAP1 0.45 0.28 0.77 0.32 20 Sphere Titania Al(OH)₃ FFA1 27 Example 9Flaky Al FAS1 0.46 0.28 0.78 0.32 20 Sphere Talc FAS1 26 Example 10Flaky Al FAS2 0.48 0.29 0.82 0.32 20 Sphere Talc FAS2 26 Example 11Flaky Al FAP1 0.63 0.39 1.10 0.63 30 Sphere Al(OH)₃ FFA1 29 Example 12Flaky Al FAP1 0.69 0.41 1.13 0.77 40 Sphere Al(OH)₃ FAP1 29 Example 13Flaky Al FAP1 0.63 0.38 1.19 0.63 30 Sphere Iron oxide FAP1 26 Example14 Flaky Al FAP1 0.42 0.25 0.68 0.30 15 Sphere Carbon Ca FFA1 21 Example15 Flaky Ni49.5Fe50.5 LAP 1.35 0.74 2.16 0.96 40 Sphere PTFE — 43Example 16 Flaky SUS316L LEP 1.65 0.89 2.58 1.23 50 Sphere Silica FAS136 Example 17 Flaky Al OTS 2.16 1.18 3.51 1.91 20 Sphere Titania FFA1 31Example 18 Flaky Al FFA1 0.52 0.32 0.86 0.33 20 Sphere Silica FAS2 36Example 19 Flaky Al IS1 0.46 0.28 0.78 0.32 20 Sphere Al(OH)₃ FFA1 29Example 20 Flaky Al AP1 0.46 0.28 0.78 0.32 20 Sphere Silica IS1 36Comparative Flaky Al FAP1 0.45 0.28 0.77 0.32 20 — — — — Example 1Comparative Flaky Al FAP1 0.45 0.28 0.77 0.32 20 Sphere FA-1 — 1 Example2 Comparative Flaky Al FAP1 0.45 0.28 0.77 0.32 20 Sphere PTFE — 55Example 3 Comparative Flaky Al FAP1 0.45 0.28 0.77 0.32 20 Sphere FA-1 —7 Example 4

TABLE 2 Thixotropy Metal suppressing Substance powder Polymerizablecompound agent A Content Content Content Content ratio [parts ratio[parts ratio [parts ratio [parts by mass] by mass] by mass] by mass]Example 1 1.5 AMO/PEA/THFA 50.9/20.0/16.9 T1 0.5 A1 0.2 Example 2 1.5AMO/THFA 41.2/44.1 T1 2.0 A1 0.8 Example 3 1.5 AMO/THFA 41.6/44.5 T2 1.2A1 0.8 Example 4 3.0 BLA/THFM/ 55.3/5.0/ T1 1.0 A3 0.7 TAOEI/DCPTeOEA/2.8/11.0/ AA/PEA/DPGDA 5.0/3.9/3.9 Example 5 1.3 AM/PMPM/TMPM/3.8/7.8/3.0/ T3 1.2 A4 1.2 MAM/EAM/DCPTeA/ 3.0/3.1/3.2/ AMO/TPGDA/VEEA58.8/1.2/2.0 Example 6 5.0 DCPTeOEM/MLM/ 3.4/3.4/ T4 0.7 A1 1.0DMTCDDA/AMO/ 2.4/41.9/ TBA/CHM/PEA/HPPA 8.6/8.4/9.9/4.9 Example 7 2.0DMDCPTA/DCPTeM/ 2.0/4.5/ T1 1.0 A1 0.5 DCPTaM/IBM/CHA/ 5.5/5.9/2.6/PEA/BA/AMO 4.0/17.0/45.0 Example 8 1.5 BLA/AMO/ 29.6/35.6/ T1 1.0 A2 0.8PEA/HBA/THFA 9.7/8.2/3.2 Example 9 1.5 BLA/AMO/ 25.1/35.0/ T5 0.3 A1 1.4VC/VP 7.2/19.3 Example 1.5 BLA/AMO/ 27.4/33.1/ T5 0.4 A1 0.4 10TBA/VEEA/UA 4.8/9.5/12.5 Example 1.5 BLA/AMO/ 33.1/35.3/ T6 0.5 A3 0.811 VP/PEA/BLM 3.5/13.9/3.0 Example 1.5 BLA/AMO/ 28.0/25.9/ T6 0.5 A1 0.212 VEEA/BM/UA 10.2/17.0/10.3 Other components Content ratio [parts η2 −ηl η0 η1 − η0 by mass] [mPa · s] [mPa · s] [mPa · s] η1/η0ll Example 1ic819/scTPO/ 4.0/4.0/ 0.2 6.9 3.3 1.04 scDETX/LF-1 1.0/1.0 Example 2ic819/scTPO/ 4.0/4.0/ 0.2 5.8 0.3 1.05 scDETX/LHP/LF-2 0.4/1.0/1.0Example 3 ic819/scTPO/ 4.0/4.0/ 0.3 5.8 0.2 1.03 scDETX/LHP/LF-20.4/1.0/1.0 Example 4 ic819/scTPO/ 4.0/4.0/ 0.5 7.8 0.5 1.06 BYK350/MEHQ0.2/0.2 Example 5 ic819/scTPO/ 4.0/4.0/ 0.6 9.2 1.0 1.11scDETX/BYK350/MEHQ 0.4/1.5/0.5 Example 6 ic819/scTPO/ 4.0/4.0/ 1.3 9.70.6 1.06 scDETX/BYK350/MEHQ 0.4/1.5/0.5 Example 7 ic819/scTPO/ 4.0/4.0/0.3 7.3 0.6 1.08 scDETX/LF-2 1.0/1.0 Example 8 ic819/scTPO/ 4.0/4.0/ 1.27.2 0.5 1.07 scDETX/BYK350/MEHQ 0.4/1.5/0.5 Example 9 ic819/scTPO/4.0/4.0/ 1.8 5.1 0.6 1.12 scDETX/LHP/LF-2 0.2/1.0/1.0 Exampleic819/scTPO/ 4.0/4.0/ 0.4 6.9 0.7 1.10 10 scDETX/BYK350/MEHQ 0.4/1.5/0.5Example ic819/scTPO/ 4.0/4.0/ 0.2 7.2 0.3 1.04 11 LHP/LF-2 0.2/0.2Example ic819/scTPO/ 4.0/2.0/ 0.15 6.0 0.2 1.03 12 LF-2/MEHQ 0.2/0.2

TABLE 3 Thixotropy Metal suppressing Substance powder Polymerizablecompound agent A Content Content Content Content ratio [parts ratio[parts ratio [parts ratio [parts by mass] by mass] by mass] by mass]Example 13 2.0 AMO/THFA/ 34.5/31.6/ T7 0.2 A4 1.2 PEA 20.1 Example 142.0 DAI/TAI/ 2.3/2.2/ T7 1.0 A1 1.0 ECA/MTEGA/ 17.6/15.1/ IBA/BA5.9/42.5 Example 15 2.0 AMO/THFA/ 28.8/27.1/ T1 1.0 A2 0.8 BA/VEEA/UA14.6/11.3/4.0 Example 16 2.0 AMO/THFA/ 27.7/28.6/ T1 1.0 A1 0.2VEEA/BM/MEDOLA 11.0/15.3/4.0 Example 17 2.5 AMO/THFA/BM 52.0/30.0/4.5 T50.3 A2 0.3 Example 18 1.5 AMO/THFA/BA 41.0/39.4/6.9 T6 0.5 A2 0.3Example 19 1.5 AMO/BA/DCPTaA/ 34.0/21.2/ T7 0.5 A2 0.3 CHDOLA 16.0/16.1Example 20 1.5 AMO/THFA 52.2/33.9 T1 1.0 A1 1.0 Comparative 1.5AMO/PEA/THFA 51.0/20.4/16.9 — — A1 0.2 Example 1 Comparative 1.5AMO/PEA/THFA 48.5/19.4/16.9 T6 3.5 A1 0.2 Example 2 Other componentsContent ratio [parts η2 − ηl η0 η1 − η0 by mass] [mPa · s] [mPa · s][mPa · s] η1/η0 Example 13 ic819/scTPO/ 4.0/4.0/ 2.7 5.6 0.9 1.16scDETX/LF-2/MEHQ 2.0/0.2/0.2 Example 14 ic819/scTPO/ 4.0/4.0/ 0.4 4.80.4 1.08 scDETX/BYK350/MEHQ 2.0/0.2/0.2 Example 15 ic819/scTPO/ 4.0/4.0/0.3 4.7 0.1 1.02 scDETX/LHP/MEHQ 2.0/0.2/0.2 Example 16 ic819/scTPO/4.0/4.0/ 0.4 7.4 0.5 1.07 scDETX/LHP 2.0/0.2 Example 17 ic819/scTPO/4.0/4.0/ 0.7 5.6 0.3 1.05 scDETX/LHP/LF-1 2.0/0.2/0.2 Example 18ic819/scTPO/ 4.0/4.0/ 0.2 4.8 0.1 1.02 scDETX/LHP/LF-1 2.0/0.2/0.2Example 19 ic819/scTPO/ 4.0/4.0/ 0.6 7.4 0.3 1.04 scDETX/LHP/LF-12.0/0.2/0.2 Example 20 ic819/scTPO/ 4.0/4.0/ 1.0 5.6 0.5 1.09scDETX/LHP/LF-1 2.0/0.2/0.2 Comparative ic819/scTPO/ 4.0/4.0/ 12.5 7.52.5 1.33 Example 1 scDETX/LF-1 1.0/1.0 Comparative ic819/scTPO/ 4.0/4.0/13.3 7.4 1.8 1.24 Example 2 scDETX/LF-1 1.0/1.0

2. Discharge Stability of Ultraviolet-Curable Composition

Firstly, a liquid droplet discharging apparatus installed in a chamber(thermal chamber) and the compositions for producing the recorded matterin each of the Examples and Comparative Examples were prepared and, in astate where the driving waveforms of piezoelectric elements wereoptimized, at a voltage 3 V higher than the use voltage, and in anenvironment of 25° C. and 50% RH, the discharge average speed of theliquid droplets and the weight of ink for each of the compositions forproducing the recorded matter were measured beforehand while carryingout continuous discharge at a frequency of 20 kHz from each nozzle of aliquid droplet discharging head of which the size of the nozzle hole hasa diameter of 22 μm. Next, the situation at the time when continuousdischarge of 1,000,000 liquid droplets (1,000,000 droplets) from eachnozzle was performed was taken in to a computer as an imaging image andthe defective nozzles (the total number of nozzles which did notnormally discharge, such as discharge speed decreases or the like whichaccompanies omissions, discharge bending, ink weight changes, and thelike) were acquired and counted. The omissions in this case indicate astate where the liquid droplets did not come out from the nozzle holesor abnormal emissions were caused in a spray form, additionally, thedischarge bending indicates a state of flying bending in a range of ±5degrees or more with respect to a normal state where discharge iscarried out in the normal direction of a nozzle surface. For thereduction of the discharge speed, a nozzle is calculated as a defectivenozzle when the speed is reduced by 3% or more with respect to thedischarge average speed calculated beforehand. When the probability ofthe generation (the ratio of defect nozzles with respect to the totalnumber of evaluated nozzles) of defective nozzles is small, thedischarge stability can be determined as high.

2.1. Bending Failure Generation Rate

A: Bending failure generation probability is less than 0.5%

B: Bending failure generation probability is 0.5% or more and less than1.0%

C: Bending failure generation probability is 1.0% or more and less than5.0%

D: Bending failure generation probability is 5.0% or more and less than10.0%

E: Bending failure generation probability is 10.0% or more

2.2. Omission Failure Generation Rate (Discharge Omission)

A: Omission failure generation probability is less than 0.5%

B: Omission failure generation probability is 0.5% or more and less than1.0%

C: Omission failure generation probability is 1.0% or more and less than2.0%

D: Omission failure generation probability is 2.0% or more and less than5.0%

E: Omission failure generation probability is 5.0% or more

3. Storage Stability Evaluation (Long Term Stability Evaluation) ofUltraviolet-Curable Composition 3.1. Dispersibility

The ultraviolet-curable compositions in each Example and ComparativeExample, were left in an environment of 40° C. for 60 days, then 1 Lthereof was passed through a capsule filter (manufactured byYamashin-Filter Corp.) with a filtration precision of 3 μm, the massconcentrations of the metal powder in the ultraviolet-curablecomposition before and after the passing were measured, the loss due tothe filtering of rough particles caused by insufficient dispersion wasdetermined using the mass concentration reduction ratio, and evaluationthereof was carried out according to the criteria below.

A: Ink concentration reduction ratio is less than 5%

B: Ink concentration reduction ratio is 5% or more and less than 10%

C: Ink concentration reduction ratio is 10% or more and less than 20%

D: Ink concentration reduction ratio is 20% or more and less than 40%

E: Ink concentration reduction ratio is 40% or more

3.2. Increase Ratio of Viscosity

The ultraviolet-curable compositions in each Example and ComparativeExample were left in an environment of 60° C. for 20 days, then theviscosity at 25° C. of the ultraviolet-curable composition in eachExample measured on the basis of JIS 28809 was measured using avibration-type viscometer, the increase ratio of the viscosity directlyafter being produced was determined, and evaluation thereof was carriedout according to the criteria below.

A: Viscosity increase ratio is less than 5%

B: Viscosity increase ratio is 5% or more and less than 10%

C: Viscosity increase ratio is 10% or more and less than 18%

D: Viscosity increase ratio is 18% or more and less than 23%

E: Viscosity increase ratio is 23% or more, or the generation of foreignmatter is confirmed

4. Producing Recorded Matter

Using the ultraviolet-curable compositions in each Example andComparative Example, interior panels were respectively produced as therecorded matter as described below.

Firstly, the ultraviolet-curable composition was inserted in an ink jetapparatus.

After that, the ultraviolet-curable composition was discharged onto asubstrate (a recording medium), which had a curved surface portionformed using polycarbonate (produced by Asahi Glass Co., Ltd., carboglass, polish, 2 mm thickness), in a predetermined pattern. The liquiddroplet discharge was performed in a state where the driving waveformsof the piezoelectric elements were optimized, at a specified voltage (28V), in an environment of 25° C. and 50% RH, and in a state where thevibration frequency (frequency) of the piezoelectric elements was 16kHz.

After that, ultraviolet rays with a spectrum which had maximum values inthe wavelengths of 365 nm, 380 nm, and 395 nm were irradiated at anirradiation intensity of 160 mW/cm² for 10 seconds and theultraviolet-curable compositions on the substrate were cured. Afterthat, heating was carried out at 80° C. for one hour and interior panelswere obtained as a recorded matter.

Using the method described above, each of the 10 interior panels(recorded matter) was produced using the ultraviolet-curablecompositions in each Example and Comparative Example.

In addition, the 10 interior panels (recorded matter) were each producedusing the ultraviolet-curable compositions in each Example andComparative Example in the same manner as described above apart fromusing a substrate formed using polyethylene terephthalate (produced byMitsubishi Plastics Inc., Diafoil G440E, 38 μm thickness), a substrateformed using a low density polyethylene (produced by Mitsui ChemicalsTohcello. Inc., T.U.X (L-LDPE) HC-E #80), a substrate formed usingbiaxial-stretched polypropylene (produced by Mitsui Chemicals Tohcello.Inc., OP U-1 #60), and a substrate formed using hard vinyl chloride(produced by Acrysunday Co., Ltd. Sunday sheet (transparent), 0.5 mmthickness), as the substrate.

5. Evaluation of Recorded Matter

Each recorded matter which was obtained as described above was evaluatedas follows.

5.1. Appearance Evaluation of Recorded Matter

Each recorded matter which was produced in each Example and ComparativeExample was visually observed and evaluated according to the criteria ofthe 7 stages below.

A: Having glossiness with a full sense of luxury and having an extremelyexcellent appearance

B: Having glossiness with a full sense of luxury and having a veryexcellent appearance

C: Having glossiness with a full sense of luxury and having an excellentappearance

D: Having glossiness with a full sense of luxury and having a favorableappearance

E: Glossiness is poor and the appearance is slightly defective

F: Glossiness is poor and the appearance is defective

G: Glossiness is poor and the appearance is extremely defective

5.2. Glossiness Level

For the pattern forming portions of each recorded matter produced ineach Example and Comparative Example, the glossiness level at a flapangle of 60° was measured using a gloss meter (MINOLTA MULTI GLOSS 268)and evaluated according to the criteria below.

A: Glossiness level is 320 or more

B: Glossiness level is 250 or more and less than 320

C: Glossiness level is 150 or more and less than 250

D: Glossiness level is less than 150

5.3. Abrasion Resistance

On the basis of JIS L0849, 48 hours after producing the recorded matter,loads of 500 g of the recorded matter according to each Example andComparative Example were mounted in a fastness test apparatus and clothrubbing was performed thereon 30 times, the glossiness level (at a flapangle 60°) of the recorded matter after the cloth rubbing was alsomeasured with the same method as the description 5.2. described above,the decrease ratio of the glossiness level before and after the clothrubbing was obtained, and evaluation thereof was carried out accordingto the criteria below.

A: Glossiness level decrease ratio is less than 10%

B: Glossiness level decrease ratio is 10% or more and less than 20%

C: Glossiness level decrease ratio is 20% or more and less than 30%

D: Glossiness level decrease ratio is 30% or more and less than 50%

E: Glossiness level decrease ratio is 50% or more

The results are shown in Table 4. Here, in Table 4, the recorded matterproduced using a substrate made of polycarbonate is shown as “M1”, therecorded matter produced using a substrate made of polyethyleneterephthalate as “M2”, the recorded matter produced using a substratemade of low density polyethylene as “M3”, the recorded matter producedusing a substrate made of biaxial-stretched polypropylene as “M4”, andthe recorded matter produced using a substrate made of hard vinylchloride as “M5”.

TABLE 4 Storage Appearance stability of recorded Abrasion DischargeDischarge Increase ratio matter Glossiness resistance bending omissionsDispersibility of viscosity M1 M2 M3 M4 M5 M1 M2 M3 M4 M5 M1 M2 M3 M4 M5Example 1 A A A A A A A B A A A A A A B B B B B Example 2 A A A A A A BB A A A A B A B B B C B Example 3 B B A A A A B C B B B B C B B B C C BExample 4 C C A B A B B B A B C C C C A A B B A Example 5 B C A B B B BB A C C C C C B B B B A Example 6 C C A B B B B C B C C C C C A B B B AExample 7 A B A B A B B B B C C C C C A B B B A Example 8 A B A B A B BC B B B C C B A B B B B Example 9 A A A C B B C B B A A B B A B A A B BExample 10 A B A B B B B B B B B C C B A A B B A Example 11 A B A C B BB B B B B B B B B B B B B Example 12 A A A A B B B C B B B B B B B B B BB Example 13 B A B B B B C C B A A B B A B B B C B Example 14 A A B B BB C B B B B C C B B B B B B Example 15 B C B B A A B C B C C C C B B B BB B Example 16 C C A A B B C C B C C C C B A B B C B Example 17 B C B BB B C C C B B C C B B B B C B Example 18 B B A A A A A B A B A B B A B BB C B Example 19 C C A A A A B A A A B B B B A A B B A Example 20 A A AA A A A B A A A B B A B B B C B Comparative C D A A C C E E D B B B B BB C D D B Example 1 Comparative E E C E E E E E E D D D D C B C D D BExample 2

As is clear from Table 4, the composition (the ultraviolet-curablecomposition) of the invention is excellent in the liquid dropletdischarge stability. In addition, the composition (theultraviolet-curable composition) of the invention is also excellent inthe storage stability. In addition, the recorded matter of the inventionhas excellent glossiness and appearance and is also excellent in theabrasion resistance of the pattern forming portion. In addition, byusing the composition (the ultraviolet-curable composition) of theinvention, excellent results were stably obtained regardless of the typeof the recording medium. In contrast, satisfactory results were notobtained with the Comparative Examples.

1. An ink composition comprising: a polymerizable compound; a metalpowder subjected to a surface treatment using a fluorine-based surfacetreatment agent, a content of the metal powder in the ink compositionbeing 0.9 mass % to 29 mass %; and; and a thixotropy suppressing agentcontaining a phosphoric acid-based dispersing agent.
 2. The inkcomposition according to claim 1, wherein the thixotropy suppressingagent further includes at least one of an alkyl amine-based dispersingagent and a fluorine-containing powder.
 3. The ink composition accordingto claim 1, wherein the content of the thixotropy suppressing agent inthe ink composition is 0.2 mass % to 2.0 mass %.
 4. The ink compositionaccording to claim 1, wherein the fluorine-based surface treatment agentis at least one selected from the group comprising a fluorine-basedsilane compound, a fluorine-based phosphate compound, afluorine-substituted fatty acid, and a fluorine-based isocyanatecompound.
 5. The ink composition according to claim 1, wherein theaverage particle diameter of the metal powder is 200 nm to 3.0 μm. 6.The ink composition according to claim 1, wherein the metal powderincludes constituent particles where at least a surface thereof includesAl.
 7. The ink composition according to claim 1, wherein the constituentparticles of the metal powder are flaky.
 8. The ink compositionaccording to claim 7, wherein an average thickness of the constituentparticles of the metal powder is 10 nm to 80 nm.
 9. The ink compositionaccording to claim 1, wherein a monomer having an alicyclic structure isincluded as the polymerizable compound.
 10. The ink compositionaccording to claim 9, wherein the monomer having the alicyclic structureincludes at least one selected from a group comprisingtris(2-acryloyloxyethyl) isocyanurate, dicyclopentenyloxyethyl acrylate,adamantyl acrylate, γ-butyrolactone acrylate, N-vinylcaprolactam,N-vinylpyrrolidone, pentamethylpiperidyl acrylate, tetramethyl piperidylacrylate, 2-methyl-2-adamantyl acrylate, 2-ethyl-2-adamantyl acrylate,mevalonic lactone acrylate, dimethylol tricyclodecane diacrylate,dimethylol dicyclopentane diacrylate, dicyclopentenyl acrylate,dicyclopentanyl acrylate, isobornyl acrylate, cyclohexyl acrylate,acryloylmorpholine, tetrahydrofurfuryl acrylate, cyclohexanespiro-2-(1,3-dioxolan-4-yl) methyl acrylate, and(2-methyl-2-ethyl-1,3-dioxolan-4-yl) methyl acrylate.
 11. The inkcomposition according to claim 1, wherein the polymerizable compound isat least one monomer selected from a group comprising phenoxyethylacrylate, benzyl acrylate, 2-(2-vinyloxyethoxy) ethyl acrylate,dipropylene glycol diacrylate, tripropylene glycol diacrylate, 2-hydroxy3-phenoxypropyl acrylate, and 4-hydroxybutyl acrylate.
 12. Recordedmatter comprising: a cured product of the ink composition according toclaim 1; and a recording medium.
 13. The ink composition according toclaim 1, further comprising a substance A which has a partial structurewhich is shown by Formula (8):

where R1 indicates an oxygen atom, a hydrogen atom, a hydrocarbon group,or an alkoxyl group and R2, R3, R4, and R5 each independently indicate ahydrogen atom or a hydrocarbon group.